Phosphate fertilizers and methods of making and using the same

ABSTRACT

A water-insoluble phosphate fertilizer, methods of producing, and methods of using the same are provided. The fertilizer may comprise at least one alkaline earth metal selected from calcium and magnesium and optionally at least one nutrient ion selected from the group consisting of potassium, ammonium, zinc, iron, manganese, copper, boron, chlorine, iodine, molybdenum or selenium. The fertilizer compounds are preferably water-insoluble, dilute acid-soluble, and free-flowing powders.

FIELD OF THE INVENTION

The present invention generally relates to fertilizers and, inparticular, to water-insoluble, slow-release phosphate fertilizers.

BACKGROUND OF THE INVENTION

Phosphates are macronutrients generally thought to be essential buildingblocks for plants and animals. Plant fertilization with phosphates,alone or in combination with nitrogen and potash fertilization,generally results in better crop yields and more nutritious food.

Prior phosphate fertilizers include diammonium phosphate (DAP),monoammonium phosphate (MAP), triple super phosphate (TSP) and others.These water-soluble compounds, however, tend to leach from the soil,leading some to apply an amount that is several times the actual cropuptake, leading to poor efficiency and the contamination of waterbodies.

SUMMARY OF THE INVENTION

Among the various aspects of the present invention is the provision ofphosphate fertilizers; the provision of water-insoluble phosphatefertilizers, the provision of dilute acid-soluble fertilizers, theprovision of phosphate fertilizers optionally containing at least onenutrient ion selected from the group consisting of potassium, sodium,ammonium, boron, chromium, cobalt, copper, iodine, iron, manganese,molybdenum, selenium, sulfur and zinc. In a preferred embodiment, thephosphate fertilizers are in the form of free-flowing powders.

Briefly, therefore, the present invention is further directed to awater-insoluble, dilute acid-soluble inorganic polyphosphate compositionin solid crystalline form, the inorganic polyphosphate compositioncontaining 5 to 70 wt % orthophosphate and having a number average chainlength of at least 2 phosphate units when the orthophosphate content ofthe polyphosphate polymer is excluded from the average chain lengthcalculation.

The present invention is further directed to a water-insoluble, diluteacid-soluble inorganic polyphosphate composition in solid crystallineform, the inorganic polyphosphate composition containing 5 to 70 wt %orthophosphate and having a number average chain length of at least 1.2phosphate units when the orthophosphate content of the polyphosphatepolymer is included in the average chain length calculation.

The present invention is further directed to a water-insoluble, diluteacid-soluble inorganic polyphosphate composition in solid crystallineform, the inorganic polyphosphate composition containing calcium,magnesium or a combination thereof, 5 to 70 wt % orthophosphate, andoptionally one or more micronutrient metals selected from the groupconsisting of chromium, cobalt, copper, iron, manganese, and zinc, withthe proviso that the inorganic polyphosphate composition contains nomore than 5 wt. % of the micronutrient metal(s), in combination, and nomore than 3.5 wt % iron when iron is the only micronutrient. Theinorganic polyphosphate polymer has a number average chain length ofmore than 2 but less than 50 repeat units when the orthophosphatecontent of the inorganic polyphosphate polymer is excluded from theaverage chain length calculation and a number average chain length of atleast 1.1 but less than 50 repeat units when the orthophosphate contentof the inorganic polyphosphate polymer is included in the average chainlength calculation, the repeat units comprising phosphate, sulfate,borate, molybdate, or selenate units, or a combination thereof, providedthe ratio of phosphate units to the combined total of sulfate, borate,molybdate and selenate repeat units comprised by the inorganicpolyphosphate composition is at least 2:1. Iron may be considered to bethe only micronutrient when the composition comprises no more than 0.01wt. % of each of chromium, cobalt, copper, manganese, and zinc.

The present invention is further directed to a water-insoluble, diluteacid-soluble inorganic polyphosphate composition in solid crystallineform, the inorganic polyphosphate composition containing at least 15 wt.% calcium, magnesium or a combination thereof, 5 to 70 wt %orthophosphate, and optionally one or more micronutrient metals selectedfrom the group consisting of chromium, cobalt, copper, iron, manganese,and zinc, with the proviso that the inorganic polyphosphate compositioncontains no more than 3.5 wt % iron when iron is the only micronutrient,no more than 7 wt. % manganese when manganese is the only micronutrient,and no more than 11 wt. % copper when copper is the only micronutrient.The inorganic polyphosphate polymer composition has a number averagechain length of more than 2 but less than 50 repeat units when theorthophosphate content of the inorganic polyphosphate polymercomposition is excluded from the average chain length calculation and anumber average chain length of at least 1.1 but less than 50 repeatunits when the orthophosphate content of the inorganic polyphosphatepolymer composition is included in the average chain length calculation,the repeat units comprising phosphate, sulfate, borate, molybdate, orselenate units, or a combination thereof, provided the ratio ofphosphate units to the combined total of sulfate, borate, molybdate andselenate repeat units comprised by the inorganic polyphosphatecomposition is at least 2:1. Iron may be considered to be the onlymicronutrient when the composition comprises no more than 0.01 wt. % ofeach of chromium, cobalt, copper, manganese, and zinc. Manganese may beconsidered to be the only micronutrient when the composition comprisesno more than 0.01 wt. % of each of chromium, cobalt, copper, iron, andzinc. Copper may be considered to be the only micronutrient when thecomposition comprises no more than 0.01 wt. % of each of chromium,cobalt, iron, manganese, and zinc.

The present invention is further directed to a water-insoluble, diluteacid-soluble inorganic polyphosphate composition in solid form, theinorganic polyphosphate composition containing at least 7 wt. % but notmore than 35 wt. % of calcium and magnesium, in combination, and lessthan 5 wt. % of boron, chromium, cobalt, copper, iodine, iron,manganese, molybdenum, selenium, sulfur and zinc, in combination. In onesuch embodiment, the inorganic polyphosphate composition contains atleast 7 wt. % but not more than 25 wt. % of calcium and magnesium, incombination

The present invention is further directed to a water-insoluble, diluteacid-soluble inorganic polyphosphate composition in solid form, theinorganic polyphosphate composition containing calcium, magnesium, or acombination thereof, and optionally one or more micronutrients selectedfrom boron, chromium, cobalt, copper, iodine, iron, manganese,molybdenum, selenium, sulfur and zinc, the inorganic polyphosphatehaving a ratio, A:P, having a value of 0.3:1 to 1.25:1 wherein A is thecombined number of equivalents of calcium and magnesium incorporated inthe inorganic polyphosphate composition and P is the number ofequivalents of phosphorous, P, incorporated in the inorganicpolyphosphate composition.

The present invention is further directed to an inorganic polyphosphatecomposition in solid form, the inorganic polyphosphate compositioncontaining at least 7 wt. % but not more than 35 wt. % of calcium andmagnesium, in combination, and optionally, one or more nutrientsselected from boron, chromium, cobalt, copper, iodine, iron, manganese,molybdenum, selenium, sulfur and zinc, the inorganic polyphosphatecomposition having a solubility in room-temperature (25° C.) deionizedwater such that the combined amount of calcium, chromium, cobalt,copper, iron, magnesium, manganese, selenium and zinc that dissolvesfrom the inorganic polyphosphate composition during a 30 minute periodin deionized water at room-temperature (25° C.) is less than 20% of thecombined amount of calcium, chromium, cobalt, copper, iron, magnesium,manganese, selenium and zinc that dissolves from the inorganicpolyphosphate composition during a 30 minute period in 0.1 N HCl atroom-temperature (25° C.). In one such embodiment, the inorganicpolyphosphate composition contains at least 7 wt. % but not more than 25wt. % of calcium and magnesium, in combination.

The present invention is further directed to an inorganic polyphosphatecomposition in solid form, the inorganic polyphosphate compositioncontaining at least 7 wt. % but not more than 35 wt. % of calcium andmagnesium, in combination, and optionally, one or more nutrientsselected from boron, chromium, cobalt, copper, iodine, iron, manganese,molybdenum, selenium and zinc, the inorganic polyphosphate compositionhaving a solubility in room-temperature (25° C.) deionized water suchthat the amount of phosphorus that dissolves from the inorganicpolyphosphate composition during a 30 minute period in deionized waterat room-temperature (25° C.) is less than 30 wt. % of the phosphorusthat dissolves from the inorganic polyphosphate composition during a 30minute period in 0.1N HCl at room-temperature (25° C.). In one suchembodiment the amount of phosphorus that dissolves from the inorganicpolyphosphate composition during a 30 minute period in deionized waterat room-temperature (25° C.) is less than 25 wt. % of the phosphorusthat dissolves from the inorganic polyphosphate composition during a 30minute period in 0.1N HCl at room-temperature (25° C.). In another suchembodiment the amount of phosphorus that dissolves from the inorganicpolyphosphate composition during a 30 minute period in deionized waterat room-temperature (25° C.) is less than 20 wt. % of the phosphorus,less than 15 wt. % that dissolves from the inorganic polyphosphatecomposition during a 30 minute period in 0.1N HCl at room-temperature(25° C.). In one such embodiment, the inorganic polyphosphatecomposition contains at least 7 wt. % but not more than 25 wt. % ofcalcium and magnesium, in combination.

The present invention is further directed to an inorganic polyphosphatecomposition in solid form, the inorganic polyphosphate compositioncontaining at least 7 wt. % but not more than 35 wt. % of calcium andmagnesium, in combination, and optionally, one or more nutrientsselected from boron, chromium, cobalt, copper, iodine, iron, manganese,molybdenum, selenium and zinc, the inorganic polyphosphate compositionhaving a solubility in room-temperature (25° C.) dilute citric acid suchthat the combined amount of calcium, chromium, cobalt, copper, iron,magnesium, manganese, selenium and zinc that dissolves from theinorganic polyphosphate composition during a 20 minute period in citricacid having a citric acid concentration not in excess of 2 wt. % citricacid at room-temperature (25° C.) is at least 75% of the combined amountof calcium, chromium, cobalt, copper, iron, magnesium, manganese,selenium and zinc that dissolves from the inorganic polyphosphatecomposition during a 20 minute period in 0.1N HCl at room-temperature(25° C.). In one such embodiment, the inorganic polyphosphatecomposition contains at least 7 wt. % but not more than 25 wt. % ofcalcium and magnesium, in combination.

The present invention is further directed to an inorganic polyphosphatecomposition in solid form, the inorganic polyphosphate compositioncontaining at least 7 wt. % but not more than 35 wt. % of calcium andmagnesium, in combination, and optionally, one or more nutrientsselected from boron, chromium, cobalt, copper, iodine, iron, manganese,molybdenum, selenium and zinc, the inorganic polyphosphate compositionhaving a solubility in room-temperature (25° C.) dilute citric acid suchthat the combined amount of calcium, chromium, cobalt, copper, iron,magnesium, manganese, selenium and zinc that dissolves from theinorganic polyphosphate composition during a 20 minute period in 0.2 wt.% citric acid at room-temperature (25° C.) is at least 75% of thecombined amount of calcium, chromium, cobalt, copper, iron, magnesium,manganese, selenium and zinc that dissolves from the inorganicpolyphosphate composition during a 20 minute period in 0.1N HCl atroom-temperature (25° C.). In one such embodiment, the inorganicpolyphosphate composition contains at least 7 wt. % but not more than 25wt. % of calcium and magnesium, in combination.

The present invention is further directed to an inorganic polyphosphatecomposition in solid form, the inorganic polyphosphate compositioncontaining at least 7 wt. % but not more than 35 wt. % of calcium andmagnesium, in combination, and optionally, one or more nutrientsselected from boron, chromium, cobalt, copper, iodine, iron, manganese,molybdenum, selenium and zinc, the inorganic polyphosphate compositionhaving a solubility in room-temperature (25° C.) dilute citric acid suchthat the combined amount of calcium, chromium, cobalt, copper, iron,magnesium, manganese, selenium and zinc that dissolves from theinorganic polyphosphate composition during a 20 minute period in 0.1 wt.% citric acid at room-temperature (25° C.) is at least 75% of thecombined amount of calcium, chromium, cobalt, copper, iron, magnesium,manganese, selenium and zinc that dissolves from the inorganicpolyphosphate composition during a 20 minute period in 0.1N HCl atroom-temperature (25° C.). In one such embodiment, the inorganicpolyphosphate composition contains at least 7 wt. % but not more than 25wt. % of calcium and magnesium, in combination.

The present invention is further directed to an inorganic polyphosphatecomposition in solid form, the inorganic polyphosphate compositioncontaining at least 7 wt. % but not more than 35 wt. % of calcium andmagnesium, in combination, and optionally, one or more nutrientsselected from boron, chromium, cobalt, copper, iodine, iron, manganese,molybdenum, selenium and zinc, the inorganic polyphosphate compositionhaving a solubility in room-temperature (25° C.) diluteethylenediaminetetraacetic acid (EDTA) such that the combined amount ofcalcium, chromium, cobalt, copper, iron, magnesium, manganese, seleniumand zinc that dissolves from the inorganic polyphosphate compositionduring a 20 minute period in 0.005M EDTA at room-temperature (25° C.) isat least 75% of the combined amount of calcium, chromium, cobalt,copper, iron, magnesium, manganese, selenium and zinc that dissolvesfrom the inorganic polyphosphate composition during a 20 minute periodin 0.1N HCl at room-temperature (25° C.). In one such embodiment, theinorganic polyphosphate composition contains at least 7 wt. % but notmore than 25 wt. % of calcium and magnesium, in combination.

The present invention is further directed to an inorganic polyphosphatecomposition in solid form, the inorganic polyphosphate compositioncontaining at least 7 wt. % but not more than 35 wt. % of calcium andmagnesium, in combination, and optionally, one or more nutrientsselected from boron, chromium, cobalt, copper, iodine, iron, manganese,molybdenum, selenium and zinc, the inorganic polyphosphate compositionhaving a solubility in room-temperature (25° C.) dilute hydrochloricacid such that the combined amount of calcium, chromium, cobalt, copper,iron, magnesium, manganese, selenium and zinc that dissolves from theinorganic polyphosphate composition during a 20 minute period in 0.01 NHCl at room-temperature (25° C.) is at least 75% of the combined amountof calcium, chromium, cobalt, copper, iron, magnesium, manganese,selenium and zinc that dissolves from the inorganic polyphosphatecomposition during a 20 minute period in 0.1N HCl at room-temperature(25° C.). In one such embodiment, the inorganic polyphosphatecomposition contains at least 7 wt. % but not more than 25 wt. % ofcalcium and magnesium, in combination.

The present invention is further directed to an inorganic polyphosphatecomposition in solid form, the inorganic polyphosphate compositioncontaining at least 7 wt. % but not more than 35 wt. % of calcium andmagnesium, in combination, and optionally, one or more nutrientsselected from boron, chromium, cobalt, copper, iodine, iron, manganese,molybdenum, selenium and zinc, the inorganic polyphosphate compositionhaving a solubility in room-temperature (25° C.) dilute citric acid,dilute ethylenediaminetetraacetic acid (EDTA), and dilute hydrochloricacid such that the combined amount of calcium, chromium, cobalt, copper,iron, magnesium, manganese, selenium and zinc that dissolves from theinorganic polyphosphate composition during a 20 minute period in each of0.1 wt. % citric acid, 0.2 wt. % citric acid, 0.005M EDTA and 0.01 N HClat room-temperature (25° C.) is at least 75% of the combined amount ofcalcium, chromium, cobalt, copper, iron, magnesium, manganese, seleniumand zinc that dissolves from the inorganic polyphosphate compositionduring a 20 minute period in 0.1N HCl at room-temperature (25° C.). Inone such embodiment, the inorganic polyphosphate composition contains atleast 7 wt. % but not more than 25 wt. % of calcium and magnesium, incombination.

Another aspect of the present invention is an inorganic polyphosphatecomposition in solid form comprising a calcium magnesium polyphosphatecomposition in solid crystalline form, characterized by having an X-raydiffraction reflection at one or more of the following positions: 5.96(±0.03), 5.37 (±0.03), 5.01 (±0.025), 4.73, 4.61, 4.5, 4.15, 4.04, 3.7,3.66(±0.01), 3.58(±0.01), 3.47(±0.01), 3.39(±0.01), 3.35(±0.01),3.19(±0.01), 3.13(±0.01), 3.09(±0.01), 3.05(±0.01), 2.96(±0.009),2.94(±0.009), 2.82(±0.009), 2.76(±0.008), 2.73(±0.008), 2.59(±0.007),2.53(±0.007), 2.5(±0.007), 2.43(±0.007), 2.41(±0.007), 2.37(±0.007),2.34(±0.006), 2.25(±0.006), 2.2(±0.006), 2.18(±0.005), 2.16(±0.005),2.14(±0.005), 2.12(±0.005), 2.09(±0.005), 2.08(±0.005), 2.03(±0.005),1.99(±0.004), 1.93(±0.004), 1.91(±0.004), 1.85(±0.003), 1.8(±0.003),1.76(±0.003), 1.72(±0.003), 1.68(±0.0028), 1.64(±0.0027), 1.59(±0.0025),1.57(±0.0024) Å.

Another aspect of the present invention is an inorganic polyphosphatecomposition in solid crystalline form comprising a calcium magnesiumpolyphosphate composition, characterized by having an X-ray diffractionreflection at one or more of the following positions: 7.54(±0.03),6.74(±0.03), 5.96 (±0.03), 5.37 (±0.03), 5.01 (±0.025), 4.73, 4.61, 4.5,4.15, 4.04, 3.7, 3.66(±0.01), 3.58(±0.01), 3.47(±0.01), 3.39(±0.01),3.35(±0.01), 3.19(±0.01), 3.13(±0.01), 3.09(±0.01), 3.05(±0.01),2.96(±0.009), 2.94(±0.009), 2.82(±0.009), 2.76(±0.008), 2.73(±0.008),2.59(±0.007), 2.53(±0.007), 2.5(±0.007), 2.43(±0.007), 2.41(±0.007),2.37(±0.007), 2.34(±0.006), 2.25(±0.006), 2.2(±0.006), 2.18(±0.005),2.16(±0.005), 2.14(±0.005), 2.12(±0.005), 2.09(±0.005), 2.08(±0.005),2.03(±0.005), 1.99(±0.004), 1.93(±0.004), 1.91(±0.004), 1.85(±0.003),1.8(±0.003), 1.76(±0.003), 1.72(±0.003), 1.68(±0.0028), 1.64(±0.0027),1.59(±0.0025), 1.57(±0.0024) Å.

The present invention is further directed to an inorganic polyphosphatecomposition in solid form, the inorganic polyphosphate compositioncomprising one or more micronutrient metal(s) selected from the groupconsisting of chromium, cobalt, copper, iron, manganese, zinc andcombinations thereof and phosphate, sulfate, borate, molybdate, orselenate repeat units, or a combination thereof, provided that the ratioof phosphate repeat units to the combined total of sulfate, borate,molybdate and selenate repeat units is at least 2:1. Thewater-insoluble, dilute acid-soluble inorganic polyphosphate compositionhas a ratio, M:Z, that is less than 0.4:1 wherein M is the combinednumber of equivalents of the micronutrient metal(s) in thewater-insoluble, dilute acid-soluble inorganic polyphosphate compositionand Z is the combined number of equivalents of phosphorous, sulfur,boron, molybdenum and selenium incorporated into the phosphate, sulfate,borate, molybdate or selenate repeat units. In one such embodiment, M:Zis less than 0.35:1.

The present invention is further directed to an inorganic polyphosphatecomposition in solid form, the inorganic polyphosphate compositioncomprising one or more micronutrient metal(s) selected from the groupconsisting of chromium, cobalt, copper, iron, manganese, zinc andcombinations thereof with the ratio of the combined number ofequivalents of the micronutrient metal(s), M, to the number ofequivalents of phosphorous, P, in the micronutrient metal polyphosphatecomposition having a value of M:P wherein M:P is less than 0.4:1. In onesuch embodiment, M:P is less than 0.35:1.

The present invention is further directed to a water-insoluble, diluteacid-soluble inorganic polyphosphate composition in solid form, theinorganic polyphosphate composition containing calcium, magnesium, or acombination thereof, and less than 5 wt. % of boron, chromium, cobalt,copper, iodine, iron, manganese, molybdenum, selenium and zinc, incombination, wherein the inorganic polyphosphate composition is afree-flowing powder having a particle size distribution that issubstantially less than 80 mesh BS.

The present invention is further directed to a water-insoluble, diluteacid-soluble inorganic polyphosphate composition in solid form, theinorganic polyphosphate composition containing calcium, magnesium, or acombination thereof, and less than 5 wt. % of boron, chromium, cobalt,copper, iodine, iron, manganese, molybdenum, selenium and zinc, incombination, the inorganic polyphosphate composition being afree-flowing powder having a moisture content of less than 10 wt. %. Inone such embodiment the moisture content is less than 15 wt %. Inanother embodiment the moisture content is less than 20 wt. %.

Another aspect of the present invention is a fertilizer compositioncomprising the inorganic polyphosphate composition described in any ofthe preceding paragraphs.

Another aspect of the invention is a method of producing an inorganicpolyphosphate composition described in any of the preceding paragraphs.The method comprises combining (i) one or more sources of at least oneof calcium and magnesium, (ii) phosphoric acid, and optionally, (iii)water to form a first mixture, and heating the first mixture to atemperature between about 80° C. and about 200° C. In one embodiment,the first mixture is heated to a temperature between about 80° C. and130° C. The heated mixture is then preferably neutralized, for examplewith calcium oxide or, alternatively, hydroxides or carbonates ofmagnesium, ammonium, potassium or sodium.

Another aspect of the invention is a method of producing the inorganicpolyphosphate composition described in any of the preceding paragraphs.The method comprises combining (i) one or more sources of at least oneof calcium and magnesium, (ii) one or more sources of one or moremicronutrients selected from boron, chromium, cobalt, copper, iodine,iron, manganese, molybdenum, potassium, seleniurri, sulfur and zinc,(iii) phosphoric acid, and optionally, (iv) water to form a firstmixture, and heating the first mixture to a temperature between about80° C. and about 200° C. In one embodiment, the first mixture is heatedto a temperature between about 80° C. and 130° C. The heated mixture isthen preferably neutralized, for example with calcium oxide or,alternatively, hydroxides or carbonates of magnesium, ammonium,potassium or sodium.

Another aspect of the invention is a method of producing the inorganicpolyphosphate composition described in any of the preceding paragraphs.The method comprises combining (i) one or more sources of at least oneof calcium and magnesium, (ii) one or more sources of one or moremicronutrients selected from boron, chromium, cobalt, copper, iodine,iron, manganese, molybdenum, potassium, selenium, sulfur, and zinc,(iii) phosphoric acid, and optionally, (iv) water to form a firstmixture, and heating the first mixture to a temperature between about80° C. and about 200° C. In one embodiment, the first mixture is heatedto a temperature between about 80° C. and 130° C. One or more sources ofone or more micronutrients selected from boron, chromium, cobalt,copper, iodine, iron, manganese, molybdenum, selenium, and zinc arecombined with the heated first mixture to form a second mixture, and thesecond mixture is heated to a temperature between about 70° C. and about200° C. In one embodiment, the second mixture is heated to a temperaturebetween about 80° C. and 130° C. The heated second mixture is thenpreferably neutralized, for example with calcium oxide or,alternatively, hydroxides or carbonates of magnesium, ammonium,potassium or sodium.

Another aspect of the invention is a method of producing the inorganicpolyphosphate composition described in any of the preceding paragraphs.The method comprises combining (i) one or more sources of at least oneof calcium and magnesium, (ii) one or more sources of one or moremicronutrients selected from boron, chromium, cobalt, copper, iodine,iron, manganese, molybdenum, potassium, selenium, sulfur and zinc, (iii)phosphoric acid, and optionally, (iv) water to form a first mixture, andheating the first mixture to a temperature between about 80° C. andabout 200° C. In one embodiment, the first mixture is heated to atemperature between about 80° C. and 130° C. The heated mixture is thenpreferably neutralized, for example with calcium oxide or,alternatively, hydroxides or carbonates of magnesium, ammonium,potassium or sodium.

Another aspect of the present invention is a method of preparing afertilizer comprising combining a polyphosphate composition described inany of preceding paragraphs or elsewhere herein with a macronutrientfertilizer, carrier or diluent.

Another aspect of the present invention is a method of fertilizing soilcomprising applying a polyphosphate composition described in any of thepreceding paragraphs or elsewhere herein to the soil.

Another aspect of the present invention is feeding a polyphosphatecomposition described in any of the preceding paragraphs or elsewhereherein to an animal.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Polyphosphate Compositions

The present invention is directed to water-insoluble, diluteacid-soluble inorganic polyphosphate polymeric compositions, fertilizerscomprising such compositions, and methods of making and using suchcompositions. In general, the polyphosphate composition comprisescalcium, magnesium or a combination thereof and, optionally, at leastone micronutrient (also sometimes referred to herein as nutrients ornutrient ions) selected from among ammonium, boron, chromium, cobalt,copper, iodine, iron, manganese, molybdenum, potassium, selenium,sodium, sulfur, zinc, and combinations thereof. In a preferredembodiment, the water-insoluble, dilute acid-soluble inorganicpolyphosphate polymeric compositions are in solid crystalline form.

In general, the inorganic polyphosphate compositions are relativelyshort-chain crystalline polyphosphates produced by incompletepolymerization of orthophosphates. Typically, therefore, the inorganicpolyphosphate will contain at least about 5 wt. % orthophosphate.Although the inorganic polyphosphate may contain as much as 70 wt. %orthophosphate, it is generally preferred that the inorganicpolyphosphate comprise substantially less. Thus, for example, in oneembodiment the inorganic polyphosphate may contain 5 to 50 wt. %orthophosphate. By way of further example, in one embodiment theinorganic polyphosphate may contain 7.5 to 50 wt. % orthophosphate. Byway of further example, in one embodiment the inorganic polyphosphatemay contain 10 to 45 wt. % orthophosphate. By way of further example, insome embodiments, the inorganic polyphosphate may contain 7.5 to 30 wt.% orthophosphate. By way of further example, in some embodiments, theinorganic polyphosphate may contain 10 to 30 wt. % orthophosphate. Byway of further example, in some embodiments, the inorganic polyphosphatemay contain 15 to 30 wt. % orthophosphate. By way of further example, insome embodiments, the inorganic polyphosphate may contain 10 to 25 wt. %orthophosphate. By way of further example, in some embodiments, theinorganic polyphosphate may contain 15 to 25 wt. % orthophosphate.

The inorganic polyphosphate compositions contain phosphate repeat unitsand may optionally also contain sulfate, borate, molybdate or selenaterepeat units, or a combination thereof. Typically, the ratio ofphosphate repeat units to the combined total of sulfate, borate,molybdate and selenate repeat units in the inorganic polyphosphatecomposition is at least 2:1(phosphate:sulfate+borate+molybdate+selenate). For example, in certainembodiments, the ratio of phosphate repeat units to the combined totalof sulfate, borate, molybdate and selenate repeat units in the inorganicpolyphosphate composition is at least 2.5:1. By way of further example,in some embodiments the ratio of phosphate repeat units to the combinedtotal of sulfate, borate, molybdate and selenate repeat units in theinorganic polyphosphate composition is at least 3:1. By way of furtherexample, in some embodiments the ratio of phosphate repeat units to thecombined total of sulfate, borate, molybdate and selenate repeat unitsin the inorganic polyphosphate composition will be between 2:1 and 5:1.By way of further example, in some embodiments the ratio of phosphaterepeat units to the combined total of sulfate, borate, molybdate andselenate repeat units in the inorganic polyphosphate composition will bebetween 2:1 and 10:1. By way of further example, in some embodiments theratio of phosphate repeat units to the sulfate repeat units in theinorganic polyphosphate composition will be between 2:1 and 5:1. By wayof further example, in some embodiments the ratio of phosphate repeatunits to the sulfate repeat units in the inorganic polyphosphatecomposition will be between 2:1 and 10:1.

Depending upon the extent of polymerization, the inorganicpolyphosphates may have a range of chain lengths. When the calculationis based upon total phosphate content (i.e., including theorthophosphate content of the polyphosphate), the average chain length(number average) may be in the range of about 1.1 and 50 repeat units(phosphate, sulfate, borate, molybdate and/or selenate repeat units) perchain. For example, in one embodiment the average chain length (numberaverage) may be 1.2 to 25 repeat units (phosphate, sulfate, borate,molybdate and/or selenate repeat units) per chain based upon totalphosphate content. By way of further example, in one embodiment theaverage chain length (number average) may be 1.2 to 20 repeat units(phosphate, sulfate, borate, molybdate and/or selenate repeat units) perchain based upon total phosphate content. By way of further example, inone embodiment the average chain length (number average) may be 1.2 to15 repeat units (phosphate, sulfate, borate, molybdate and/or selenaterepeat units) per chain based upon total phosphate content. By way offurther example, in one embodiment the average chain length (numberaverage) may be 2 to 20 repeat units (phosphate, sulfate, borate,molybdate and/or selenate repeat units) per chain based upon totalphosphate content. By way of further example, in one embodiment theaverage chain length (number average) may be 2 to 15 repeat units(phosphate, sulfate, borate, molybdate and/or selenate repeat units) perchain based upon total phosphate content. By way of further example, inone embodiment the average chain length (number average) may be 2 to 10repeat units (phosphate, sulfate, borate, molybdate and/or selenaterepeat units) per chain based upon total phosphate content. By way offurther example, in one embodiment the average chain length (numberaverage) may be 2.5 to 15 repeat units (phosphate, sulfate, borate,molybdate and/or selenate repeat units) per chain based upon totalphosphate content. By way of further example, in one embodiment theaverage chain length (number average) may be 2.5 to 10 repeat units(phosphate, sulfate, borate, molybdate and/or selenate repeat units) perchain based upon total phosphate content. By way of further example, inone embodiment the average chain length (number average) may be 3 to 15repeat units (phosphate, sulfate, borate, molybdate and/or selenaterepeat units) per chain based upon total phosphate content. By way offurther example, in one embodiment the average chain length (numberaverage) may be 3 to 10 repeat units (phosphate, sulfate, borate,molybdate and/or selenate repeat units) per chain based upon totalphosphate content. By way of further example, in one embodiment theaverage chain length (number average) may be 1.2 to 5 repeat units(phosphate, sulfate, borate, molybdate and/or selenate repeat units) perchain based upon total phosphate content. By way of further example, inone embodiment the average chain length (number average) may be 1.3 to 4repeat units (phosphate, sulfate, borate, molybdate and/or selenaterepeat units) per chain based upon total phosphate content. By way offurther example, in one embodiment the average chain length (numberaverage) may be 1.3 to 2.9 repeat units (phosphate, sulfate, borate,molybdate and/or selenate repeat units) per chain based upon totalphosphate content.

In certain embodiments, when the calculation is based upon totalphosphate content (i.e., including the orthophosphate content of thepolyphosphate), the average chain length (number average) may be in therange of about 1.1 and 50 phosphate units (phosphorus atoms) per chain.For example, in one embodiment the average chain length (number average)may be 1.2 to 25 phosphate units (phosphorus atoms) per chain based upontotal phosphate content. By way of further example, in one embodimentthe average chain length (number average) may be 1.2 to 20 phosphateunits (phosphorus atoms) per chain based upon total phosphate content.By way of further example, in one embodiment the average chain length(number average) may be 1.2 to 15 phosphate units (phosphorus atoms) perchain based upon total phosphate content. By way of further example, inone embodiment the average chain length (number average) may be 2 to 20phosphate units (phosphorus atoms) per chain based upon total phosphatecontent. By way of further example, in one embodiment the average chainlength (number average) may be 2 to 15 phosphate units (phosphorusatoms) per chain based upon total phosphate content. By way of furtherexample, in one embodiment the average chain length (number average) maybe 2 to 10 phosphate units (phosphorus atoms) per chain based upon totalphosphate content. By way of further example, in one embodiment theaverage chain length (number average) may be 2.5 to 15 phosphate units(phosphorus atoms) per chain based upon total phosphate content. By wayof further example, in one embodiment the average chain length (numberaverage) may be 2.5 to 10 phosphate units (phosphorus atoms) per chainbased upon total phosphate content. By way of further example, in oneembodiment the average chain length (number average) may be 3 to 15phosphate units (phosphorus atoms) per chain based upon total phosphatecontent. By way of further example, in one embodiment the average chainlength (number average) may be 1.2 to 5 phosphate units (phosphorusatoms) per chain based upon total phosphate content. By way of furtherexample, in one embodiment the average chain length (number average) maybe 1.3 to 4 phosphate units (phosphorus atoms) per chain based upontotal phosphate content. By way of further example, in one embodimentthe average chain length (number average) may be 1.3 to 2.9 phosphateunits (phosphorus atoms) per chain based upon total phosphate content.

When the calculation is based upon the non-orthophosphate fraction ofthe polyphosphate, (i.e., excluding the orthophosphate fraction of thepolyphosphate from the calculation), the average chain length (numberaverage) may be in the range of about 2 and the average chain length(number average) may be in the range of about 1.2 and 50 repeat units(phosphate, sulfate, borate, molybdate and/or selenate repeat units) perchain based upon the non-orthophosphate fraction of the polyphosphate.For example, in one embodiment the average chain length (number average)may be 1.2 to 25 repeat units (phosphate, sulfate, borate, molybdateand/or selenate repeat units) per chain based upon thenon-orthophosphate fraction of the polyphosphate. By way of furtherexample, in one embodiment the average chain length (number average) maybe 1.2 to 20 repeat units (phosphate, sulfate, borate, molybdate and/orselenate repeat units) per chain based upon the non-orthophosphatefraction of the polyphosphate. By way of further example, in oneembodiment the average chain length (number average) may be 1.2 to 15repeat units (phosphate, sulfate, borate, molybdate and/or selenaterepeat units) per chain based upon the non-orthophosphate fraction ofthe polyphosphate. By way of further example, in one embodiment theaverage chain length (number average) may be 2 to 20 repeat units(phosphate, sulfate, borate, molybdate and/or selenate repeat units) perchain based upon the non-orthophosphate fraction of the polyphosphate.By way of further example, in one embodiment the average chain length(number average) may be 2 to 15 repeat units (phosphate, sulfate,borate, molybdate and/or selenate repeat units) per chain based upon thenon-orthophosphate fraction of the polyphosphate. By way of furtherexample, in one embodiment the average chain length (number average) maybe 2 to 10 repeat units (phosphate, sulfate, borate, molybdate and/orselenate repeat units) per chain based upon the non-orthophosphatefraction of the polyphosphate. By way of further example, in oneembodiment the average chain length (number average) may be 2.5 to 15repeat units (phosphate, sulfate, borate, molybdate and/or selenaterepeat units) per chain based upon the non-orthophosphate fraction ofthe polyphosphate. By way of further example, in one embodiment theaverage chain length (number average) may be 2.5 to 10 repeat units(phosphate, sulfate, borate, molybdate and/or selenate repeat units) perchain based upon the non-orthophosphate fraction of the polyphosphate.By way of further example, in one embodiment the average chain length(number average) may be 3 to 15 repeat units (phosphate, sulfate,borate, molybdate and/or selenate repeat units) per chain based upon thenon-orthophosphate fraction of the polyphosphate. By way of furtherexample, in one embodiment the average chain length (number average) maybe 3 to 10 repeat units (phosphate, sulfate, borate, molybdate and/orselenate repeat units) per chain based upon the non-orthophosphatefraction of the polyphosphate. By way of further example, in oneembodiment the average chain length (number average) may be 2.1 to 10repeat units (phosphate, sulfate, borate, molybdate and/or selenaterepeat units) per chain based upon the non-orthophosphate fraction ofthe polyphosphate. By way of further example, in one embodiment theaverage chain length (number average) may be 2.5 to 7 repeat units(phosphate, sulfate, borate, molybdate and/or selenate repeat units) perchain based upon the non-orthophosphate fraction of the polyphosphate.By way of further example, in one embodiment the average chain length(number average) may be 2.5 to 5 repeat units (phosphate, sulfate,borate, molybdate and/or selenate repeat units) per chain based upon thenon-orthophosphate fraction of the polyphosphate.

In some embodiments in which the calculation is based upon thenon-orthophosphate fraction of the polyphosphate, (i.e., excluding theorthophosphate fraction of the polyphosphate from the calculation), theaverage chain length (number average) may be in the range of about 2 and50 phosphate units (phosphorus atoms) per chain. For example, in oneembodiment the average chain length (number average) may be 2 to 25phosphate units (phosphorus atoms) per chain based upon thenon-orthophosphate fraction of the polyphosphate. By way of furtherexample, in one embodiment the average chain length (number average) maybe 2 to 20 phosphate units (phosphorus atoms) per chain based upon thenon-orthophosphate fraction of the polyphosphate. By way of furtherexample, in one embodiment the average chain length (number average) maybe 2 to 15 phosphate units (phosphorus atoms) per chain based upon thenon-orthophosphate fraction of the polyphosphate. By way of furtherexample, in one embodiment the average chain length (number average) maybe 2 to 10 phosphate units (phosphorus atoms) per chain based upon thenon-orthophosphate fraction of the polyphosphate. By way of furtherexample, in one embodiment the average chain length (number average) maybe 2.5 to 20 phosphate units (phosphorus atoms) per chain based upon thenon-orthophosphate fraction of the polyphosphate. By way of furtherexample, in one embodiment the average chain length (number average) maybe 2.5 to 15 phosphate units (phosphorus atoms) per chain based upon thenon-orthophosphate fraction of the polyphosphate. By way of furtherexample, in one embodiment the average chain length (number average) maybe 2.5 to 10 phosphate units (phosphorus atoms) per chain based upon thenon-orthophosphate fraction of the polyphosphate. By way of furtherexample, in one embodiment the average chain length (number average) maybe 3 to 20 phosphate units (phosphorus atoms) per chain based upon thenon-orthophosphate fraction of the polyphosphate. By way of furtherexample, in one embodiment the average chain length (number average) maybe 3 to 15 phosphate units (phosphorus atoms) per chain based upon thenon-orthophosphate fraction of the polyphosphate. By way of furtherexample, in one embodiment the average chain length (number average) maybe 3 to 10 phosphate units (phosphorus atoms) per chain based upon thenon-orthophosphate fraction of the polyphosphate. By way of furtherexample, in one embodiment the average chain length (number average) maybe 3.5 to 20 phosphate units (phosphorus atoms) per chain based upon thenon-orthophosphate fraction of the polyphosphate. By way of furtherexample, in one embodiment the average chain length (number average) maybe 3.5 to 15 phosphate units (phosphorus atoms) per chain based upon thenon-orthophosphate fraction of the polyphosphate. By way of furtherexample, in one embodiment the average chain length (number average) maybe 3.5 to 10 phosphate units (phosphorus atoms) per chain based upon thenon-orthophosphate fraction of the polyphosphate. By way of furtherexample, in one embodiment the average chain length (number average) maybe 4 to 20 phosphate units (phosphorus atoms) per chain based upon thenon-orthophosphate fraction of the polyphosphate. By way of furtherexample, in one embodiment the average chain length (number average) maybe 4 to 15 phosphate units (phosphorus atoms) per chain based upon thenon-orthophosphate fraction of the polyphosphate. By way of furtherexample, in one embodiment the average chain length (number average) maybe 4 to 10 phosphate units (phosphorus atoms) per chain based upon thenon-orthophosphate fraction of the polyphosphate. By way of furtherexample, in one embodiment the average chain length (number average) maybe 4 to 9 phosphate units (phosphorus atoms) per chain based upon thenon-orthophosphate fraction of the polyphosphate. By way of furtherexample, in one embodiment the average chain length (number average) maybe 4 to 8 phosphate units (phosphorus atoms) per chain based upon thenon-orthophosphate fraction of the polyphosphate. By way of furtherexample, in one embodiment the average chain length (number average) maybe 2.1 to 50 phosphate units (phosphorus atoms) per chain based upon thenon-orthophosphate fraction of the polyphosphate. By way of furtherexample, in one embodiment the average chain length (number average) maybe 2.1 to 10 phosphate units (phosphorus atoms) per chain based upon thenon-orthophosphate fraction of the polyphosphate. By way of furtherexample, in one embodiment the average chain length (number average) maybe 2.5 to 7 phosphate units (phosphorus atoms) per chain based upon thenon-orthophosphate fraction of the polyphosphate. By way of furtherexample, in one embodiment the average chain length (number average) maybe 2.5 to 5 phosphate units (phosphorus atoms) per chain based upon thenon-orthophosphate fraction of the polyphosphate.

On a molar basis, the polyphosphate composition also preferably containsat least 0.5 phosphate/sulfate/borate/molybdate/selenate repeat units(i.e., the combined total of phosphate, sulfate, borate, molybdate andselenate repeat units) for each atom of calcium and magnesium (incombination). In one exemplary embodiment, the polyphosphate compositioncontains at least 0.66 phosphate/sulfate/borate/molybdate/selenaterepeat units (i.e., the combined total of phosphate, sulfate, borate,molybdate and selenate repeat units) for each atom of calcium andmagnesium (in combination). By way of further example, in oneembodiment, the polyphosphate composition contains at least 0.75phosphate/sulfate/borate/molybdate/selenate repeat units for each atomof calcium and magnesium (in combination). By way of further example, inone embodiment, the polyphosphate composition contains at least 0.825phosphate/sulfate/borate/molybdate/selenate repeat units for each atomof calcium and magnesium (in combination). By way of further example, inone embodiment, the polyphosphate composition contains at least 0.95phosphate/sulfate/borate/molybdate/selenate repeat units for each atomof calcium and magnesium (in combination). By way of further example, inone embodiment, the polyphosphate composition contains no more than onealkaline earth metal atom selected from the group consisting of calcium,magnesium and a combination thereof for eachphosphate/sulfate/borate/molybdate/selenate repeat units of theinorganic polyphosphate composition. By way of further example, in oneembodiment, the polyphosphate composition contains at least 1.11phosphate/sulfate/borate/molybdate/selenate repeat units for each atomof calcium and magnesium (in combination). By way of further example, inone embodiment, the polyphosphate composition may contain about 1.33phosphate/sulfate/borate/molybdate/selenate repeat units for each atomof calcium and magnesium (in combination). By way of further example, inone embodiment, the polyphosphate composition may contain about 1.67phosphate/sulfate/borate/molybdate/selenate repeat units for each atomof calcium and magnesium (in combination). By way of further example, inone embodiment, the polyphosphate composition may contain about 2.22phosphate/sulfate/borate/molybdate/selenate repeat units for each atomof calcium and magnesium (in combination). In general, however, theupper limit of the ratio of phosphate/sulfate/borate/molybdate/selenaterepeat units to calcium and magnesium atoms is the ratio that would leadto the formation of the corresponding dihydrogen orthophosphate.

In one embodiment, on a molar basis, the polyphosphate compositionpreferably contains at least 0.5 phosphate repeat units for each atom ofcalcium and magnesium (in combination). In one exemplary embodiment, thepolyphosphate composition contains at least 0.66 phosphate units(phosphorous atom) for each atom of calcium and magnesium (incombination). By way of further example, in one embodiment, thepolyphosphate composition contains at least 0.75 phosphate units(phosphorous atom) for each atom of calcium and magnesium (incombination). By way of further example, in one embodiment, thepolyphosphate composition contains at least 0.825 phosphate units(phosphorous atom) for each atom of calcium and magnesium (incombination). By way of further example, in one embodiment, thepolyphosphate composition contains at least 0.95 phosphate units(phosphorous atom) for each atom of calcium and magnesium (incombination). By way of further example, in one embodiment, thepolyphosphate composition contains no more than one alkaline earth metalatom selected from the group consisting of calcium, magnesium and acombination thereof for each phosphate unit (phosphorous atom) of theinorganic polyphosphate composition. In one exemplary embodiment, thepolyphosphate composition contains By way of further example, in oneembodiment, the polyphosphate composition contains at least 1.11phosphate units (phosphorous atom) for each atom of calcium andmagnesium (in combination). By way of further example, in oneembodiment, the polyphosphate composition may contain about 1.33phosphate units (phosphorous atoms) for each atom of calcium andmagnesium (in combination). By way of further example, in oneembodiment, the polyphosphate composition may contain about 1.67phosphate units (phosphorous atoms) for each atom of calcium andmagnesium (in combination). By way of further example, in oneembodiment, the polyphosphate composition may contain about 2.22phosphate units (phosphorous atoms) for each atom of calcium andmagnesium (in combination). In general, however, the upper limit of theratio of phosphate units (phosphorous atoms) to calcium and magnesiumatoms is the ratio that would lead to the formation of the correspondingdihydrogen orthophosphate.

In general, it is preferred that inorganic polyphosphate compositioncontain calcium, magnesium, or a combination thereof, and that theinorganic polyphosphate have a ratio, A:Z, having a value of at least0.3:1, wherein A is the combined number of equivalents of calcium andmagnesium incorporated in the inorganic polyphosphate composition and Zis the combined number of equivalents of phosphate, sulfate, borate,molybdate, and selenate repeat units incorporated in the inorganicpolyphosphate composition. In one exemplary embodiment, A:Z is at least0.4:1. In another exemplary embodiment, A:Z is at least 0.45:1. Inanother exemplary embodiment, A:Z is at least 0.5:1. In anotherexemplary embodiment, A:Z is at least 0.52:1. In another exemplaryembodiment, A:Z is at least 0.5:1. In another exemplary embodiment, A:Zis at least 0.5:1. In another exemplary embodiment, A:Z is at least0.6:1. In another exemplary embodiment, A:Z is at least 0.5:1. Inanother exemplary embodiment, A:Z is at least 0.65:1. In anotherexemplary embodiment, A:Z is at least 0.7:1. In another exemplaryembodiment, A:Z is at least 0.5:1. In another exemplary embodiment, A:Zis at least 0.8:1. In another exemplary embodiment, A:Z is at least0.9:1. In general, however, A:Z will not exceed 1.25:1, with ratios inthe range of about 0.5:1 to about 1:1 or even about 0.5:1 to about0.75:1 being more typical. For example, in each of the foregoingembodiments, the inorganic polyphosphate composition may comprisephosphate repeat units and sulfate repeat units. By way of furtherexample, in each of the foregoing embodiments, the inorganicpolyphosphate composition may comprise phosphate repeat units andsulfate repeat units with the ratio of phosphate repeat units to sulfaterepeat units being between 10:1 and 2:1.

In some embodiments, the ratio of the number of equivalents of calciumand magnesium, in combination, for each equivalent of phosphate in thepolyphosphate composition is two-thirds of the value of thecorresponding molar ratio. Stated differently, it is generally preferredthat inorganic polyphosphate composition contain calcium, magnesium, ora combination thereof, and that the inorganic polyphosphate have aratio, A:P, having a value of at least 0.3:1, wherein A is the combinednumber of equivalents of calcium and magnesium incorporated in theinorganic polyphosphate composition and P is the number of equivalentsof phosphorous, P, incorporated in the inorganic polyphosphatecomposition. In one exemplary embodiment, A:P is at least 0.4:1. Inanother exemplary embodiment, A:P is at least 0.45:1. In anotherexemplary embodiment, A:P is at least 0.5:1. In another exemplaryembodiment, A:P is at least 0.52:1. In another exemplary embodiment, A:Pis at least 0.5:1. In another exemplary embodiment, A:P is at least0.5:1. In another exemplary embodiment, A:P is at least 0.6:1. Inanother exemplary embodiment, A:P is at least 0.5:1. In anotherexemplary embodiment, A:P is at least 0.65:1. In another exemplaryembodiment, A:P is at least 0.7:1. In another exemplary embodiment, A:Pis at least 0.5:1. In another exemplary embodiment, A:P is at least0.8:1. In another exemplary embodiment, A:P is at least 0.9:1. Ingeneral, however, A:P will not exceed 1:1, with ratios in the range ofabout 0.5:1 to about 0.75:1 being more typical.

Considered on a weight basis, it is generally preferred that theinorganic polyphosphate composition comprise at least 7 weight percentof an alkaline earth metal selected from calcium, magnesium and acombination thereof, based upon the total weight of the polyphosphate.Typically, however, the polyphosphate composition will contain less thanabout 25 weight percent of calcium and magnesium, in combination. By wayof further example, in this embodiment, the polyphosphate compositionmay contain less than 35 wt. % of calcium and magnesium, in combination.Thus, for example, in one embodiment the polyphosphate compositioncomprises at least 7 wt. % calcium and no, or only trace amounts ofmagnesium. By way of further example, in this embodiment, thepolyphosphate composition may contain at least 10 wt. % calcium and no,or only trace amounts of magnesium. By way of further example, in thisembodiment, the polyphosphate composition may contain at least 12 wt. %calcium and no, or only trace amounts of magnesium. By way of furtherexample, in this embodiment, the polyphosphate composition may containat least 15 wt. % calcium and no, or only trace amounts of magnesium. Byway of further example, in this embodiment, the polyphosphatecomposition may contain at least 20 wt. % calcium and no, or only traceamounts of magnesium. Alternatively, in one embodiment, thepolyphosphate composition comprises at least 7 wt. % magnesium and no,or only trace amounts of calcium. By way of further example, in thisembodiment, the polyphosphate composition may contain at least 10 wt. %magnesium and no, or only trace amounts of calcium. By way of furtherexample, in this embodiment, the polyphosphate composition may containat least 12 wt. % magnesium and no, or only trace amounts of calcium. Byway of further example, in this embodiment, the polyphosphatecomposition may contain at least 15 wt. % magnesium and no, or onlytrace amounts of calcium. By way of further example, in this embodiment,the polyphosphate composition may contain at least 20 wt. % magnesiumand no, or only trace amounts of calcium. In yet another embodiment, thepolyphosphate composition contains more than trace amounts of each ofcalcium and magnesium and, in combination, calcium and magnesiumconstitute at least 7 wt. % of the total weight of the composition. Forexample, in one embodiment, the polyphosphate composition contains morethan trace amounts of each of calcium and magnesium and, in combination,calcium and magnesium constitute at least 12 wt. % of the total weightof the composition. By way of further example, in one embodiment, thepolyphosphate composition contains more than trace amounts of each ofcalcium and magnesium and, in combination, calcium and magnesiumconstitute at least 15 wt. % of the total weight of the composition. Byway of further example, in one embodiment, the polyphosphate compositioncontains more than trace amounts of each of calcium and magnesium and,in combination, calcium and magnesium constitute at least 20 wt. % ofthe total weight of the composition.

In general, when the composition contains both calcium and magnesium, itis generally preferred that the atomic ratio of calcium to magnesium begreater than 0.2:1 (calcium:magnesium). For example, the atomic ratio ofcalcium to magnesium may be greater than 0.5:1 (calcium:magnesium). Incertain embodiments, the composition contains more calcium thanmagnesium. Thus, for example, the atomic ratio of calcium to magnesiummay exceed 1.25:1 (calcium:magnesium). In one such preferred embodiment,the atomic ratio of calcium to magnesium exceeds 1.5:1(calcium:magnesium). In one such preferred embodiment, the atomic ratioof calcium to magnesium exceeds 1.75:1 (calcium:magnesium). In one suchpreferred embodiment, the atomic ratio of calcium to magnesium exceeds2:1 (calcium:magnesium). In one such preferred embodiment, the atomicratio of calcium to magnesium exceeds 4:1 (calcium:magnesium). In onesuch preferred embodiment, the atomic ratio of calcium to magnesiumexceeds 5:1 (calcium:magnesium).

Advantageously, the polyphosphates of the present invention arewater-insoluble. That is, the phosphates do not appreciably dissolve indeionized water at room temperature (25° C.) water and neutral pH; forexample, the polyphosphates will not release more than 20% of thecombined amounts of calcium and magnesium contained by the polyphosphatecomposition within 10 minutes, and preferably within an hour.Water-insolubility may be conveniently assessed, for example, byreference to the dissolution of the polyphosphate in moderate strengthmineral acid. For example, the combined amounts of calcium and magnesium(and any micronutrient metals selected from the group consisting ofchromium, cobalt, copper, iron, manganese, selenium and zinc) containedby the polyphosphate composition that dissolves from the inorganicpolyphosphate composition during a 30 minute period in deionized waterat room-temperature (25° C.) is less than 20% (by weight) of thecombined amount of calcium and magnesium (and any micronutrient metalsselected chromium, cobalt, copper, iron, manganese, selenium and zinc)that dissolves from the inorganic polyphosphate composition during a 30minute period in 0.1N HCl at room-temperature (25° C.). In one preferredembodiment, the amount of such metals that dissolve in DI water is lessthan 15% of the amount of such metals that dissolve in 0.1 N HCl undersuch conditions. In one preferred embodiment, the amount of such metalsthat dissolve in DI water is less than 10% of the amount of such metalsthat dissolve in 0.1 N HCl under such conditions. In one preferredembodiment, the amount of such metals that dissolve in DI water is lessthan 9% of the amount of such metals that dissolve in 0.1N HCl undersuch conditions. In one preferred embodiment, the amount of such metalsthat dissolve in DI water is less than 8% of the amount of such metalsthat dissolve in 0.1N HCl under such conditions.

The polyphosphates dissolve relatively rapidly at room temperature indilute citric acid. Stated differently, the extent of dissolution in aone hour period in dilute citric acid, such as 2 wt. %, 1 wt. % or even0.2 wt % or 0.1 wt. % citric acid, at room temperature is a substantialfraction of the extent of dissolution in significantly stronger acidssuch as 0.1N HCl acid at room temperature. For example, the combinedamount of calcium and magnesium (and any chromium, cobalt, copper, iron,manganese, selenium and zinc) that dissolves from the inorganicpolyphosphate composition during a 20 minute period in 2 wt. % citricacid at room-temperature (25° C.) is at least 75% of the combined amountof calcium and magnesium (and any chromium, cobalt, copper, iron,manganese, selenium and zinc) that dissolves from the inorganicpolyphosphate composition during a 20 minute period in 0.1N HCl atroom-temperature (25° C.); in certain more preferred embodiments, theamount that dissolves in the 2 wt. % citric acid is at 80%, 85%, 90% oreven 95% of the combined amount of calcium and magnesium (and anychromium, cobalt, copper, iron, manganese, selenium and zinc) thatdissolves from the inorganic polyphosphate composition during a 20minute period in 0.1N HCl at room-temperature (25° C.). By way offurther example, in one embodiment the combined amount of calcium andmagnesium (and any chromium, cobalt, copper, iron, manganese, seleniumand zinc) that dissolves from the inorganic polyphosphate compositionduring a 20 minute period in 1 wt. % citric acid at room-temperature(25° C.) is at least 75% of the combined amount of calcium and magnesium(and any chromium, cobalt, copper, iron, manganese, selenium and zinc)that dissolves from the inorganic polyphosphate composition during a 20minute period in 0.1N HCl at room-temperature (25° C.); in certain morepreferred embodiments, the amount that dissolves in the 1 wt. % citricacid is at 80%, 85%, 90% or even 95% of the combined amount of calciumand magnesium (and any chromium, cobalt, copper, iron, manganese,selenium and zinc) that dissolves from the inorganic polyphosphatecomposition during a 20 minute period in 0.1N HCl at room-temperature(25° C.). By way of further example, in one embodiment the combinedamount of calcium and magnesium (and any chromium, cobalt, copper, iron,manganese, selenium and zinc) that dissolves from the inorganicpolyphosphate composition during a 20 minute period in 0.2 wt. % citricacid at room-temperature (25° C.) is at least 75% of the combined amountof calcium and magnesium (and any chromium, cobalt, copper, iron,manganese, selenium and zinc) that dissolves from the inorganicpolyphosphate composition during a 20 minute period in 0.1N HCl atroom-temperature (25° C.); in certain more preferred embodiments, theamount that dissolves in the 0.2 wt. % citric acid is at 80%, 85%, 90%or even 95% of the combined amount of calcium and magnesium (and anychromium, cobalt, copper, iron, manganese, selenium and zinc) thatdissolves from the inorganic polyphosphate composition during a 20minute period in 0.1N HCl at room-temperature (25° C.). By way offurther example, in one embodiment the combined amount of calcium andmagnesium (and any chromium, cobalt, copper, iron, manganese, seleniumand zinc) that dissolves from the inorganic polyphosphate compositionduring a 20 minute period in 0.1 wt. % citric acid at room-temperature(25° C.) is at least 75% of the combined amount of calcium and magnesium(and any chromium, cobalt, copper, iron, manganese, selenium and zinc)that dissolves from the inorganic polyphosphate composition during a 20minute period in 0.1N HCl at room-temperature (25° C.); in certain morepreferred embodiments, the amount that dissolves in the 0.1 wt. % citricacid is at 80%, 85%, 90% or even 95% of the combined amount of calciumand magnesium (and any chromium, cobalt, copper, iron, manganese,selenium and zinc) that dissolves from the inorganic polyphosphatecomposition during a 20 minute period in 0.1N HCl at room-temperature(25° C.)

In one embodiment, the polyphosphate composition preferably alsodissolves relatively rapidly at room temperature in diluteethylenediaminetetraacetic acid (EDTA). Stated differently, the extentof dissolution in a one hour period in 0.005 M EDTA is preferably asubstantial fraction of the extent of dissolution in significantlystronger acids such as 0.1 N HCl acid at room temperature. For example,the combined amount of calcium and magnesium (and any chromium, cobalt,copper, iron, manganese, selenium and zinc) that dissolves from theinorganic polyphosphate composition during a 20 minute period in 0.005MEDTA at room-temperature (25° C.) is at least 75% of the combined amountof calcium and magnesium (and any chromium, cobalt, copper, iron,manganese, selenium and zinc) that dissolves from the inorganicpolyphosphate composition during a 20 minute period in 0.1N HCl atroom-temperature (25° C.). In one preferred embodiment, the amount ofsuch metals that dissolve in 0.005M EDTA is at least 80% of the amountof such metals that dissolve in 0.1 N HCl under such conditions. In onepreferred embodiment, the amount of such metals that dissolve in 0.005MEDTA is at least 85% of the amount of such metals that dissolve in 0.1NHCl under such conditions. In one preferred embodiment, the amount ofsuch metals that dissolve in 0.005M EDTA is at least 90% of the amountof such metals that dissolve in 0.1 N HCl under such conditions. In onepreferred embodiment, the amount of such metals that dissolve in 0.005MEDTA is at least 95% of the amount of such metals that dissolve in 0.1NHCl under such conditions.

In one embodiment, the polyphosphate composition preferably alsodissolves relatively rapidly at room temperature in dilute HCl. Stateddifferently, the extent of dissolution in a one hour period in 0.01N HClat room temperature is a substantial fraction of the extent ofdissolution in significantly stronger acids such as 0.1 N HCl acid atroom temperature. For example, the combined amount of calcium andmagnesium (and any chromium, cobalt, copper, iron, manganese, seleniumand zinc) that dissolves from the inorganic polyphosphate compositionduring a 20 minute period in 0.01 N HCl at room-temperature (25° C.) isat least 75% of the combined amount of calcium and magnesium (and anychromium, cobalt, copper, iron, manganese, selenium and zinc) thatdissolves from the inorganic polyphosphate composition during a 20minute period in 0.1N HCl at room-temperature (25° C.). In one preferredembodiment, the amount of such metals that dissolve in 0.01 N HCl is atleast 80% of the amount of such metals that dissolve in 0.1N HCl undersuch conditions. In one preferred embodiment, the amount of such metalsthat dissolve in 0.01 N HCl is at least 85% of the amount of such metalsthat dissolve in 0.1 N HCl under such conditions. In one preferredembodiment, the amount of such metals that dissolve in 0.01 N HCl is atleast 90% of the amount of such metals that dissolve in 0.1N HCl undersuch conditions. In one preferred embodiment, the amount of such metalsthat dissolve in 0.01 N HCl is at least 95% of the amount of such metalsthat dissolve in 0.1N HCl under such conditions.

In one embodiment, the polyphosphate composition dissolves relativelyrapidly at room temperature in 0.2 wt. % citric acid, 0.005M EDTA and0.01N HCl. In addition, the extent of dissolution in a one hour periodin dilute acids such as 0.2 wt. % citric acid, 0.005M EDTA and 0.01N HClat room temperature is a substantial fraction of the extent ofdissolution in significantly stronger acids such as 0.1 N HCl acid atroom temperature. For example, the combined amount of calcium andmagnesium (and any chromium, cobalt, copper, iron, manganese, seleniumand zinc) that dissolves from the inorganic polyphosphate compositionduring a 20 minute period in each of 0.2 wt. % citric acid, 0.005M EDTAand 0.01 N HCl at room-temperature (25° C.) is at least 75% of thecombined amount of calcium and magnesium (and any chromium, cobalt,copper, iron, manganese, selenium and zinc) that dissolves from theinorganic polyphosphate composition during a 20 minute period in 0.1NHCl at room-temperature (25° C.). In one preferred embodiment, theamount of such metals that dissolve in each of the dilute acids is atleast 80% of the amount of such metals that dissolve in 0.1 N HCl undersuch conditions. In one preferred embodiment, the amount of such metalsthat dissolve in each of the dilute acids is at least 85% of the amountof such metals that dissolve in 0.1N HCl under such conditions. In onepreferred embodiment, the amount of such metals that dissolve in each ofthe dilute acids is at least 90% of the amount of such metals thatdissolve in 0.1N HCl under such conditions. In one preferred embodiment,the amount of such metals that dissolve in each of the dilute acids isat least 95% of the amount of such metals that dissolve in 0.1 N HClunder such conditions.

In one embodiment, the polyphosphate composition dissolves relativelyrapidly at room temperature in 0.1 wt. % citric acid, 0.005M EDTA and0.01N HCl. In addition, the extent of dissolution in a one hour periodin dilute acids such as 0.1 wt. % citric acid, 0.005M EDTA and 0.01N HClat room temperature is a substantial fraction of the extent ofdissolution in significantly stronger acids such as 0.1 N HCl acid atroom temperature. For example, the combined amount of calcium andmagnesium (and any chromium, cobalt, copper, iron, manganese, seleniumand zinc) that dissolves from the inorganic polyphosphate compositionduring a 20 minute period in each of 0.1 wt. % citric acid, 0.005M EDTAand 0.01N HCl at room-temperature (25° C.) is at least 75% of thecombined amount of calcium and magnesium (and any chromium, cobalt,copper, iron, manganese, selenium and zinc) that dissolves from theinorganic polyphosphate composition during a 20 minute period in 0.1 NHCl at room-temperature (25° C.). In one preferred embodiment, theamount of such metals that dissolve in each of the dilute acids is atleast 80% of the amount of such metals that dissolve in 0.1 N HCl undersuch conditions. In one preferred embodiment, the amount of such metalsthat dissolve in each of the dilute acids is at least 85% of the amountof such metals that dissolve in 0.1 N HCl under such conditions. In onepreferred embodiment, the amount of such metals that dissolve in each ofthe dilute acids is at least 90% of the amount of such metals thatdissolve in 0.1N HCl under such conditions. In one preferred embodiment,the amount of such metals that dissolve in each of the dilute acids isat least 95% of the amount of such metals that dissolve in 0.1N HClunder such conditions.

Depending upon their composition, certain of the polyphosphates can becharacterized by their X-ray diffraction reflections at one or more ofthe following positions: 5.96 (±0.03), 5.37 (±0.03), 5.01 (±0.025),4.73, 4.61, 4.5, 4.15, 4.04, 3.7, 3.66(±0.01), 3.58(±0.01), 3.47(±0.01),3.39(±0.01), 3.35(±0.01), 3.19(±0.01), 3.13(±0.01), 3.09(±0.01),3.05(±0.01), 2.96(±0.009), 2.94(±0.009), 2.82(±0.009), 2.76(±0.008),2.73(±0.008), 2.59(±0.007), 2.53(±0.007), 2.5(±0.007), 2.43(±0.007),2.41(±0.007), 2.37(±0.007), 2.34(±0.006), 2.25(±0.006), 2.2(±0.006),2.18(±0.005), 2.16(±0.005), 2.14(±0.005), 2.12(±0.005), 2.09(±0.005),2.08(±0.005), 2.03(±0.005), 1.99(±0.004), 1.93(±0.004), 1.91(±0.004),1.85(±0.003), 1.8(±0.003), 1.76(±0.003), 1.72(±0.003), 1.68(±0.0028),1.64(±0.0027), 1.59(±0.0025), 1.57(±0.0024) Å.

Depending upon their composition, certain of the polyphosphates can becharacterized by their X-ray diffraction reflections at one or more ofthe following positions: 7.54(±0.03), 6.74(±0.03), 5.96 (±0.03), 5.37(±0.03), 5.01 (±0.025), 4.73, 4.61, 4.5, 4.15, 4.04, 3.7, 3.66(±0.01),3.58(±0.01), 3.47(±0.01), 3.39(±0.01), 3.35(±0.01), 3.19(±0.01),3.13(±0.01), 3.09(±0.01), 3.05(±0.01), 2.96(±0.009), 2.94(±0.009),2.82(±0.009), 2.76(±0.008), 2.73(±0.008), 2.59(±0.007), 2.53(±0.007),2.5(±0.007), 2.43(±0.007), 2.41(±0.007), 2.37(±0.007), 2.34(±0.006),2.25(±0.006), 2.2(±0.006), 2.18(±0.005), 2.16(±0.005), 2.14(±0.005),2.12(±0.005), 2.09(±0.005), 2.08(±0.005), 2.03(±0.005), 1.99(±0.004),1.93(±0.004), 1.91(±0.004), 1.85(±0.003), 1.8(±0.003), 1.76(±0.003),1.72(±0.003), 1.68(±0.0028), 1.64(±0.0027), 1.59(±0.0025), 1.57(±0.0024)Å.

Advantageously, the polyphosphate composition may comprise a range ofmetals and other ions in addition to calcium, magnesium, or acombination thereof. For example, the polyphosphate composition maycomprise potassium as a nutrient ion. Typically in this embodiment, thepolyphosphate composition preferably contains less than about 20 wt. %potassium, based on the total weight of the polyphosphate composition.In this embodiment, the polyphosphate composition preferably containsless than about 15 wt. % potassium, based on the total weight of thepolyphosphate; in other such embodiments, the polyphosphate containsless than 10 wt. % potassium, less than 5 wt. % potassium, or even lessthan 1 wt. % potassium. When included, the polyphosphate will typicallycomprise about 10-15 wt. % potassium.

In one embodiment, the polyphosphate composition contains sodium (e.g.,at least about 0.01 wt. % sodium) as a nutrient ion in addition tocalcium, magnesium, or a combination thereof. In this embodiment, thepolyphosphate composition preferably contains less than about 10 wt. %sodium, based on the total weight of the polyphosphate; in other suchembodiments, the polyphosphate contains less than 7.5 wt. % sodium, lessthan 5 wt. % sodium, or even less than 1 wt. % sodium. When included,the polyphosphate will typically comprise about 1-5 wt. % sodium.

In one embodiment, the polyphosphate composition contains sulfur (e.g.,at least about 0.01 wt. % sulfur) as a nutrient ion in addition tocalcium, magnesium, or a combination thereof. In this embodiment, thepolyphosphate composition preferably contains less than about 10 wt. %sulfur, based on the total weight of the polyphosphate; in other suchembodiments, the polyphosphate contains less than 7 wt. % sulfur, lessthan 5 wt. % sulfur, or even less than 1 wt. % sulfur. When included,the polyphosphate will typically comprise about 1 to 7 wt. % sulfur.

In one embodiment, the polyphosphate composition contains ammonium(e.g., at least about 0.01 wt. % ammonium) as a nutrient ion in additionto calcium, magnesium, or a combination thereof. In this embodiment, thepolyphosphate composition preferably contains less than about 10 wt. %ammonium, based on the total weight of the polyphosphate; in other suchembodiments, the polyphosphate contains less than 7.5 wt. % ammonium,less than 5 wt. % ammonium, or even less than 1 wt. % ammonium. Whenincluded, the polyphosphate will typically comprise about 1-5 wt. %ammonium.

In one embodiment, the polyphosphate composition contains zinc (e.g., atleast about 0.01 wt. % zinc) as a nutrient ion in addition to calcium,magnesium, or a combination thereof. In this embodiment, thepolyphosphate composition preferably contains less than about 9 weightpercent zinc, based on the total weight of the polyphosphate; in othersuch embodiments, the polyphosphate contains less than 6 wt. % zinc,less than 5 wt. % zinc, less than 4 wt. % zinc, less than 3 wt. % zinc,less than 2 wt. % zinc, less than 1 wt. % zinc, less than 0.5 wt. %zinc, less than 0.25 wt. % zinc, or even less than 0.1 wt. % zinc.

In one embodiment, the polyphosphate composition contains iron (e.g., atleast about 0.01 wt. % iron) as a nutrient ion in addition to calcium,magnesium, or a combination thereof. In this embodiment, thepolyphosphate composition preferably contains less than about 6 weightpercent iron, based on the total weight of the polyphosphate; in othersuch embodiments, the polyphosphate contains less than 5 wt. % iron,less than 4 wt. % iron, less than 3 wt. % iron, less than 2 wt. % iron,less than 1 wt. % iron, less than 0.5 wt. % iron, less than 0.25 wt. %iron, or even less than 0.1 wt. % iron.

In one embodiment, the polyphosphate composition contains manganese(e.g., at least about 0.01 wt. % manganese) as a nutrient ion inaddition to calcium, magnesium, or a combination thereof. In thisembodiment, the polyphosphate composition preferably contains less thanabout 5 weight percent manganese, based on the total weight of thepolyphosphate; in other such embodiments, the polyphosphate containsless than 4 wt. % manganese, less than 3 wt. % manganese, less than 2wt. % manganese, less than 1 wt. % manganese, less than 0.5 wt. %manganese, less than 0.25 wt. % manganese, or even less than 0.1 wt. %manganese.

In one embodiment, the polyphosphate composition contains copper (e.g.,at least about 0.01 wt. % copper) as a nutrient ion in addition tocalcium, magnesium, or a combination thereof. In this embodiment, thepolyphosphate composition preferably contains less than about 12 weightpercent copper, based on the total weight of the polyphosphate; in othersuch embodiments, the polyphosphate contains less than 5 wt. % copper,less than 4 wt. % copper, less than 3 wt. % copper, less than 2 wt. %copper, less than 1 wt. % copper, less than 0.5 wt. % copper, less than0.25 wt. % copper, or even less than 0.1 wt. % copper.

In one embodiment, the polyphosphate composition contains chromium(e.g., at least about 0.01 wt. % chromium) as a nutrient ion in additionto calcium, magnesium, or a combination thereof. In this embodiment, thepolyphosphate composition preferably contains less than about 5 weightpercent chromium, based on the total weight of the polyphosphate; inother such embodiments, the polyphosphate contains less than 4 wt. %chromium, less than 3 wt. % chromium, less than 2 wt. % chromium, lessthan 1 wt. % chromium, less than 0.5 wt. % chromium, less than 0.25 wt.% chromium, or even less than 0.1 wt. % chromium.

In one embodiment, the polyphosphate composition contains cobalt (e.g.,at least about 0.01 wt. % cobalt) as a nutrient ion in addition tocalcium, magnesium, or a combination thereof. In this embodiment, thepolyphosphate composition preferably contains less than about 5 weightpercent cobalt, based on the total weight of the polyphosphate; in othersuch embodiments, the polyphosphate contains less than 4 wt. % cobalt,less than 3 wt. % cobalt, less than 2 wt. % cobalt, less than 1 wt. %cobalt, less than 0.9 wt. % cobalt, less than 0.75 wt. % cobalt, lessthan 0.5 wt. % cobalt, less than 0.25 wt. % cobalt, less than 0.1 wt. %cobalt, or even less than 0.05 wt. % cobalt.

In one embodiment, the polyphosphate composition contains selenium(e.g., at least about 0.01 wt. % selenium) as a nutrient ion in additionto calcium, magnesium, or a combination thereof. In this embodiment, thepolyphosphate composition preferably contains less than about 10 weightpercent selenium, based on the total weight of the polyphosphate; inother such embodiments, the polyphosphate contains less than 5 wt. %selenium, less than 3 wt. % selenium, less than 1 wt. % selenium, lessthan 0.5 wt. % selenium, less than 0.5 wt. % selenium, less than 0.9 wt.% selenium, less than 0.75 wt. % selenium, less than 0.5 wt. % selenium,less than 0.25 wt. % selenium, less than 0.1 wt. % selenium, or evenless than 0.05 wt. % selenium.

In one embodiment, the polyphosphate composition contains boron (e.g.,at least about 0.01 wt. % boron) as a nutrient ion in addition tocalcium, magnesium, or a combination thereof. In this embodiment, thepolyphosphate composition preferably contains less than about 10 weightpercent boron, based on the total weight of the polyphosphate; in othersuch embodiments, the polyphosphate contains less than 5 wt. % boron,less than 2 wt. % boron, less than 1.75 wt. % boron, less than 1.5 wt. %boron, less than 1.25 wt. % boron, less than 1 wt. % boron, less than0.75 wt. % boron, less than 0.5 wt. % boron, less than 0.25 wt. % boron,less than 0.1 wt. % boron, less than 0.075 wt. % boron, less than 0.05wt. % boron, less than 0.025 wt. % boron, or even about 0.01 wt. %boron.

In one embodiment, the polyphosphate composition contains iodine (e.g.,at least about 0.01 wt. % iodine) as a nutrient ion in addition tocalcium, magnesium, or a combination thereof.

In one embodiment, the polyphosphate composition contains molybdenum(e.g., at least about 0.01 wt. % molybdenum) as a nutrient ion inaddition to calcium, magnesium, or a combination thereof. In thisembodiment, the polyphosphate composition preferably contains less thanabout 10 weight percent molybdenum, based on the total weight of thepolyphosphate; in other such embodiments, the polyphosphate containsless than 5 wt. % molybdenum, less than 3 wt. % molybdenum, less than 2wt. % molybdenum, less than 1 wt. % molybdenum, less than 0.09 wt. %molybdenum, less than 0.075 wt. % molybdenum, less than 0.05 wt. %molybdenum, less than 0.025 wt. % molybdenum, or even about 0.01 wt. %molybdenum.

In one embodiment, the polyphosphate composition contains at least 0.01wt. % of at least each of two different nutrients selected from thegroup consisting of boron, chromium, cobalt, copper, iodine, iron,manganese, molybdenum, selenium and zinc. In this embodiment, thepolyphosphate composition contains less than about 15 weight percent ofsuch nutrients, combined, based on the total weight of the polyphosphatecomposition. For example, in one such embodiment, the polyphosphatecomposition contains less than about 10 weight percent of suchnutrients, combined, based on the total weight of the polyphosphatecomposition. By way of further example, in one such embodiment, thepolyphosphate composition contains less than about 7 weight percent ofsuch nutrients, combined, based on the total weight of the polyphosphatecomposition. By way of further example, in one such embodiment, thepolyphosphate composition contains less than about 6 weight percent ofsuch nutrients, combined, based on the total weight of the polyphosphatecomposition. By way of further example, in one such embodiment, thepolyphosphate composition contains less than about 5 weight percent ofsuch nutrients, combined, based on the total weight of the polyphosphatecomposition. By way of further example, in one such embodiment, thepolyphosphate composition contains less than about 4.5 weight percent ofsuch nutrients, combined, based on the total weight of the polyphosphatecomposition. By way of further example, in one such embodiment, thepolyphosphate composition contains less than about 4 weight percent ofsuch nutrients, combined, based on the total weight of the polyphosphatecomposition. By way of further example, in one such embodiment, thepolyphosphate composition contains less than about 3.5 weight percent ofsuch nutrients, combined, based on the total weight of the polyphosphatecomposition. By way of further example, in one such embodiment, thepolyphosphate composition contains less than about 3 weight percent ofsuch nutrients, combined, based on the total weight of the polyphosphatecomposition. By way of further example, in one such embodiment, thepolyphosphate composition contains less than about 2.5 weight percent ofsuch nutrients, combined, based on the total weight of the polyphosphatecomposition. By way of further example, in one such embodiment, thepolyphosphate composition contains less than about 2 weight percent ofsuch nutrients, combined, based on the total weight of the polyphosphatecomposition. By way of further example, in one such embodiment, thepolyphosphate composition contains less than about 1.5 weight percent ofsuch nutrients, combined, based on the total weight of the polyphosphatecomposition. By way of further example, in one such embodiment, thepolyphosphate composition contains less than about 1 weight percent ofsuch nutrients, combined, based on the total weight of the polyphosphatecomposition. By way of further example, in one such embodiment, thepolyphosphate composition contains less than about 0.5 weight percent ofsuch nutrients, combined, based on the total weight of the polyphosphatecomposition.

For use as a fertilizer, the polyphosphate compositions of the presentinvention may optionally contain, in addition to one or more ofammonium, boron, chromium, cobalt, copper, iodine, iron, manganese,molybdenum, potassium, selenium, sodium, sulfur and zinc, othercomponents that contribute to the nutritional, material handling, orother characteristics of the fertilizer. For example, the fertilizercomposition may contain a water-soluble N-P-K macronutrient fertilizercomposition that has been blended or otherwise combined with thealkaline earth metal polyphosphate composition. By way of furtherexample, the fertilizer may contain organic materials like plantresidues that have been blended or otherwise combined with themicronutrient metal polyphosphate composition to improve the materialhandling characteristics of the fertilizer.

In general, the alkaline earth metal polyphosphate is preferably asolid, free-flowing particulate material. Particle size is not narrowlycritical but is generally preferably less than 80 mesh BS. Stateddifferently, a mass of the particulate polyphosphate composition has asize distribution with substantially all of the particles having a sizeless than 80 mesh BS. In one embodiment, a significant fraction of theparticles have a size less than 150 mesh BS. For example, in oneembodiment the majority of the particles in a population of particlesare less than 150 mesh BS. By way of further example, in one embodimenta significant fraction of the particles may be smaller than 300 mesh BS;in one such embodiment, the particles have a size distribution withabout 20% by volume of the particles having a size less than 300 meshBS.

In general, the polyphosphate composition is preferably a solid,free-flowing particulate material with relatively low moisture content.Typically, the polyphosphate composition comprises less than 20 wt. %moisture. For example, in certain embodiments, the polyphosphatecomposition comprises less than 10 wt. % moisture. In certainembodiments, the polyphosphate composition comprises less than 8 wt. %moisture. By way of further example, in certain embodiments thepolyphosphate composition comprises less than 5 wt. % moisture. Forexample, in certain embodiments, the polyphosphate composition comprisesat least 2 wt. % moisture. By way of further example, in certainembodiments the polyphosphate composition comprises less than 4 wt. %moisture

Alkaline Earth Metal Polyphosphates

In another embodiment, the polyphosphate composition comprises calciumas the only cation (other than protons). In such embodiments, the ratioof the combined number of moles of phosphorus, sulfur, boron,molybdenum, selenium (incorporated in the phosphate, sulfate, borate,molybdate and selenate repeat units) to moles of calcium in the calciumpolyphosphate may be greater than 0.5:1, respectively. By way of furtherexample, the ratio of the moles of phosphorus, sulfur, boron,molybdenum, selenium (incorporated in the phosphate, sulfate, borate,molybdate and selenate repeat units) to moles of calcium in the calciumpolyphosphate may be greater than 0.66:1, respectively. By way offurther example, the ratio of the moles of phosphorus, sulfur, boron,molybdenum, selenium (incorporated in the phosphate, sulfate, borate,molybdate and selenate repeat units) to moles of calcium in the calciumpolyphosphate may be greater than 1.1:1, respectively. By way of furtherexample, the ratio of the moles of phosphorus, sulfur, boron,molybdenum, selenium (incorporated in the phosphate, sulfate, borate,molybdate and selenate repeat units) to moles of calcium in the calciumpolyphosphate may be greater than 1.67:1, respectively.

In certain embodiments, the ratio of the moles of phosphorus to moles ofcalcium in the calcium polyphosphate may be greater than 0.5:1,respectively. By way of further example, the ratio of the moles ofphosphorus to moles of calcium in the calcium polyphosphate may begreater than 0.66:1, respectively. By way of further example, the ratioof the moles of phosphorus to moles of calcium in the calciumpolyphosphate may be greater than 1.1:1, respectively. By way of furtherexample, the ratio of the moles of phosphorus to moles of calcium in thecalcium polyphosphate may be greater than 1.67:1, respectively.

In another embodiment, the polyphosphate composition comprises magnesiumas the only cation (other than protons). In such embodiments, the ratioof the combined number of moles of phosphorus, sulfur, boron,molybdenum, selenium (incorporated in the phosphate, sulfate, borate,molybdate and selenate repeat units) to moles of magnesium in themagnesium polyphosphate may be greater than 0.5:1, respectively. By wayof further example, the ratio of the moles of phosphorus, sulfur, boron,molybdenum, selenium (incorporated in the phosphate, sulfate, borate,molybdate and selenate repeat units) to moles of magnesium in themagnesium polyphosphate may be greater than 0.66:1, respectively. By wayof further example, the ratio of the moles of phosphorus, sulfur, boron,molybdenum, selenium (incorporated in the phosphate, sulfate, borate,molybdate and selenate repeat units) to moles of magnesium in themagnesium polyphosphate may be greater than 1.1:1, respectively. By wayof further example, the ratio of the moles of phosphorus, sulfur, boron,molybdenum, selenium (incorporated in the phosphate, sulfate, borate,molybdate and selenate repeat units) to moles of magnesium in themagnesium polyphosphate may be greater than 1.67:1, respectively.

In some embodiments, the ratio of the moles of phosphorus to moles ofmagnesium in the magnesium polyphosphate may be greater than 0.5:1,respectively. By way of further example, the ratio of the moles ofphosphorus to moles of magnesium in the magnesium polyphosphate may begreater than 0.66:1, respectively. By way of further example, the ratioof the moles of phosphorus to moles of magnesium in the magnesiumpolyphosphate may be greater than 1.1:1, respectively. By way of furtherexample, the ratio of the moles of phosphorus to moles of magnesium inthe magnesium polyphosphate may be greater than 1.67:1, respectively.

In another embodiment, the polyphosphate composition comprises calciumand magnesium as the only cations (other than protons). For example, theratio of moles of calcium to moles of magnesium may be greater than0.2:1, respectively. By way of further example, the ratio of the molesof calcium to moles of magnesium may be greater than 0.5:1,respectively. By way of further example, the ratio of the moles ofcalcium to moles of magnesium may be greater than 1:1, respectively. Byway of further example, the ratio of the moles of calcium to moles ofmagnesium may be greater than 2:1, respectively. By way of furtherexample, the ratio of moles of calcium to moles of magnesium may begreater than 4:1, respectively. By way of further example, the ratio ofthe moles of calcium to moles of magnesium may be greater than 5:1,respectively. By way of further example, the ratio of the combinednumber of moles of phosphorus, sulfur, boron, molybdenum, and selenium(incorporated in the phosphate, sulfate, borate, molybdate and selenaterepeat units) to moles of calcium and magnesium (in combination) in thepolyphosphate may be greater than 0.67:1, respectively. By way offurther example, the ratio of the combined number of moles ofphosphorus, sulfur, boron, molybdenum, and selenium (incorporated in thephosphate, sulfate, borate, molybdate and selenate repeat units) tomoles of calcium and magnesium (in combination) in the polyphosphate maybe greater than 0.74:1, respectively. By way of further example, theratio of the combined number of moles of phosphorus, sulfur, boron,molybdenum, and selenium (incorporated in the phosphate, sulfate,borate, molybdate and selenate repeat units) to moles of calcium andmagnesium (in combination) in the polyphosphate may be greater than0.83:1, respectively. By way of further example, the ratio of thecombined number of moles of phosphorus, sulfur, boron, molybdenum, andselenium (incorporated in the phosphate, sulfate, borate, molybdate andselenate repeat units) to moles of calcium and magnesium (incombination) in the polyphosphate may be greater than 0.95:1,respectively. By way of further example, the ratio of the combinednumber of moles of phosphorus, sulfur, boron, molybdenum, and selenium(incorporated in the phosphate, sulfate, borate, molybdate and selenaterepeat units) to moles of calcium and magnesium (in combination) in thepolyphosphate may be greater than 1.1:1, respectively. By way of furtherexample, the ratio of the combined number of moles of phosphorus,sulfur, boron, molybdenum, and selenium (incorporated in the phosphate,sulfate, borate, molybdate and selenate repeat units) to moles ofcalcium and magnesium (in combination) in the polyphosphate may begreater than 1.33:1, respectively. By way of further example, the ratioof the combined number of moles of phosphorus, sulfur, boron,molybdenum, and selenium (incorporated in the phosphate, sulfate,borate, molybdate and selenate repeat units) to moles of calcium andmagnesium (in combination) in the polyphosphate may be equal to 1.67.1,respectively.

In certain embodiments, the ratio of the moles of phosphorus to moles ofcalcium and magnesium (in combination) in the polyphosphate may begreater than 0.5:1, respectively. By way of further example, the ratioof the moles of phosphorus to moles of calcium and magnesium (incombination) in the polyphosphate may be greater than 0.67:1,respectively. By way of further example, the ratio of the moles ofphosphorus to moles of calcium and magnesium (in combination) in thepolyphosphate may be greater than 0.74:1, respectively. By way offurther example, the ratio of the moles of phosphorus to moles ofcalcium and magnesium (in combination) in the polyphosphate may begreater than 0.83:1, respectively. By way of further example, the ratioof the moles of phosphorus to moles of calcium and magnesium (incombination) in the polyphosphate may be greater than 0.95:1,respectively. By way of further example, the ratio of the moles ofphosphorus to moles of calcium and magnesium (in combination) in thepolyphosphate may be greater than 1.1:1, respectively. By way of furtherexample, the ratio of the moles of phosphorus to moles of calcium andmagnesium (in combination) in the polyphosphate may be greater than1.33:1, respectively. By way of further example, the ratio of the molesof phosphorus to moles of calcium and magnesium (in combination) in thepolyphosphate may be equal to 1.67.1, respectively.

In one embodiment, the polyphosphate composition comprises calcium,magnesium and one nutrient ion as the only cations (other than protons).For example, alkaline earth metal polyphosphate composition may compriseonly calcium and magnesium and zinc as the only cations (other thanprotons). By way of further example, the ratio of the combined number ofmoles of phosphorus, sulfur, boron, molybdenum and selenium incorporatedin the repeat units to moles of zinc in the polyphosphate may be greaterthan 5:1, respectively. By way of further example, the ratio of themoles of phosphorus to moles of zinc in the polyphosphate may be greaterthan 5:1, respectively. By way of further example, the ratio of thecombined number of moles of phosphorus, sulfur, boron, molybdenum andselenium incorporated in the repeat units to moles of zinc in thepolyphosphate may be greater than 10:1, respectively. By way of furtherexample, the ratio of the moles of phosphorus to moles of zinc in thepolyphosphate may be greater than 10:1, respectively. By way of furtherexample, the ratio of the combined number of moles of phosphorus,sulfur, boron, molybdenum and selenium incorporated in the repeat unitsto moles of zinc in the polyphosphate may be greater than 20:1,respectively. By way of further example, the ratio of the moles ofphosphorus to moles of zinc in the polyphosphate may be greater than20:1, respectively.

In one embodiment, the polyphosphate composition comprises calcium,magnesium and one nutrient ion as the only cations (other than protons).For example, the polyphosphate composition may comprise only calcium,magnesium and iron as the only cations (other than protons). By way offurther example, the ratio of the combined number of moles ofphosphorus, sulfur, boron, molybdenum and selenium incorporated in therepeat units to moles of iron in the polyphosphate may be greater than5:1, respectively. By way of further example, the ratio of the moles ofphosphorus to moles of iron in the polyphosphate may be greater than5:1, respectively. By way of further example, the ratio of the combinednumber of moles of phosphorus, sulfur, boron, molybdenum and seleniumincorporated in the repeat units to moles of iron in the polyphosphatemay be greater than 10:1, respectively. By way of further example, theratio of the moles of phosphorus to moles of iron in the polyphosphatemay be greater than 10:1, respectively. By way of further example, theratio of the combined number of moles of phosphorus, sulfur, boron,molybdenum and selenium incorporated in the repeat units to moles ofiron in the polyphosphate may be greater than 20:1, respectively. By wayof further example, the ratio of the moles of phosphorus to moles ofiron in the polyphosphate may be greater than 20:1, respectively.

In one embodiment, the polyphosphate composition comprises calcium,magnesium and one nutrient ion as the only cations (other than protons).For example, polyphosphate composition may comprise only calcium andmagnesium and manganese as the only cations (other than protons). By wayof further example, the ratio of the combined number of moles ofphosphorus, sulfur, boron, molybdenum and selenium incorporated in therepeat units to moles of manganese in the polyphosphate may be greaterthan 5:1, respectively. By way of further example, the ratio of themoles of phosphorus to moles of manganese to in the polyphosphate may begreater than 5:1, respectively. By way of further example, the ratio ofthe combined number of moles of phosphorus, sulfur, boron, molybdenumand selenium incorporated in the repeat units to moles of manganese inthe polyphosphate may be greater than 10:1, respectively. By way offurther example, the ratio of the moles of phosphorus to moles ofmanganese to in the polyphosphate may be greater than 10:1,respectively. By way of further example, the ratio of the combinednumber of moles of phosphorus, sulfur, boron, molybdenum and seleniumincorporated in the repeat units to moles of manganese in thepolyphosphate may be greater than 20:1, respectively. By way of furtherexample, the ratio of the moles of phosphorus to moles of manganese inthe polyphosphate may be greater than 20:1, respectively.

In one embodiment, the alkaline earth metal polyphosphate compositioncomprises calcium, magnesium and one nutrient ion as the only cations(other than protons). For example, alkaline earth metal polyphosphatecomposition may comprise calcium, magnesium and boron as the onlycations (other than protons). By way of further example, the ratio ofthe moles of phosphorus to moles of boron to in the polyphosphate may begreater than 2:1, respectively. By way of further example, the ratio ofthe moles of phosphorus to moles of boron to in the polyphosphate may begreater than 5:1, respectively. By way of further example, the ratio ofthe moles of phosphorus to moles of boron to in the polyphosphate may begreater than 10:1, respectively. By way of further example, the ratio ofthe moles of phosphorus to moles of boron in the polyphosphate may begreater than 20:1, respectively.

In one embodiment, the alkaline earth metal polyphosphate compositioncomprises calcium, magnesium and one nutrient ion as the only cations(other than protons). For example, alkaline earth metal polyphosphatecomposition may comprise calcium, magnesium and copper as the onlycations (other than protons). By way of further example, the ratio ofthe combined number of moles of phosphorus, sulfur, boron, molybdenumand selenium incorporated in the repeat units to moles of copper in thepolyphosphate may be greater than 5:1, respectively. By way of furtherexample, the ratio of the moles of phosphorus to moles of copper in thepolyphosphate may be greater than 5:1, respectively. By way of furtherexample, the ratio of the combined number of moles of phosphorus,sulfur, boron, molybdenum and selenium incorporated in the repeat unitsto moles of copper in the polyphosphate may be greater than 10:1,respectively. By way of further example, the ratio of the moles ofphosphorus to moles of copper in the polyphosphate may be greater than10:1, respectively. By way of further example, the ratio of the combinednumber of moles of phosphorus, sulfur, boron, molybdenum and seleniumincorporated in the repeat units to moles of copper in the polyphosphatemay be greater than 20:1, respectively. By way of further example, theratio of the moles of phosphorus to moles of copper in the polyphosphatemay be greater than 20:1, respectively.

In one embodiment, the alkaline earth metal polyphosphate compositioncomprises calcium, magnesium, and one nutrient ion as the only cations(other than protons). For example, alkaline earth metal polyphosphatecomposition may comprise calcium, magnesium and selenium as the onlycations (other than protons). By way of further example, the ratio ofthe moles of phosphorus to moles of selenium in the polyphosphate may begreater than 2:1, respectively. By way of further example, the ratio ofthe moles of phosphorus to moles of selenium in the polyphosphate may begreater than 5:1, respectively. By way of further example, the ratio ofthe moles of phosphorus to moles of selenium in the polyphosphate may begreater than 10:1, respectively. By way of further example, the ratio ofthe moles of phosphorus to moles of selenium in the polyphosphate may begreater than 20:1, respectively.

More generally, in certain embodiments the ratio of the moles ofphosphorus to moles of nutrient ions (selected from among boron,chromium, cobalt, copper, iodine, iron, manganese, molybdenum, selenium,sulfur and zinc) will be greater than 2:1, respectively. For example, inone embodiment in which the polyphosphate comprises two or more nutrientions (selected from among boron, chromium, cobalt, copper, iodine, iron,manganese, molybdenum, selenium and zinc), the ratio of the moles ofphosphorus to moles of the nutrient ions will be greater than 5:1,respectively. For example, in one embodiment in which the polyphosphatecomprises two or more nutrient ions (selected from among boron,chromium, cobalt, copper, iodine, iron, manganese, molybdenum, seleniumand zinc), the ratio of the moles of phosphorus to moles of the nutrientions will be greater than 10:1, respectively. For example, in oneembodiment in which the polyphosphate comprises two or more nutrientions (selected from among boron, chromium, cobalt, copper, iodine, iron,manganese, molybdenum, selenium, sulfur and zinc), the ratio of themoles of phosphorus to moles of the nutrient ions will be greater than20:1, respectively.

As described elsewhere herein, the polyphosphate compositions may beneutralized post-polymerization for improved material handlingcharacteristics. In general, it is preferred that the equilibrium pH ofan aqueous mixture of ten parts by weight of water at neutral pH and onepart by weight of the neutralized polyphosphate be at least pH 2. Morepreferably, the equilibrium pH of an aqueous mixture of ten parts byweight of water at neutral pH and one part by weight of the neutralizedpolyphosphate be at least pH 3. Still more preferably, the equilibriumpH of an aqueous mixture of ten parts by weight of water at neutral pHand one part by weight of the neutralized polyphosphate be at least pH4. Still more preferably, the equilibrium pH of an aqueous mixture often parts by weight of water at neutral pH and one part by weight of theneutralized polyphosphate be at least pH 5. In certain embodiments, theequilibrium pH of an aqueous mixture of ten parts by weight of water atneutral pH and one part by weight of the neutralized polyphosphate be atleast pH 6. For example, in one embodiment, the equilibrium pH of anaqueous mixture of ten parts by weight of water at neutral pH and onepart by weight of the neutralized polyphosphate will be in the range ofpH 4-8.

Calcium Polyphosphate Compositions

In one embodiment, the polyphosphate composition of the presentinvention comprises calcium as a cation. In general, polyphosphatecompositions containing calcium as a cation contain at least 7 wt. %calcium. Typically, polyphosphate compositions containing calcium as acation contain at least 10 wt. % calcium. In certain embodiments,polyphosphate compositions containing calcium as a cation contain atleast 13 wt. % calcium. In certain embodiments, polyphosphatecompositions containing calcium as a cation contain at least 15 wt. %calcium. In other embodiments, polyphosphate compositions containingcalcium as a cation contain at least 20 wt. % calcium. In otherembodiments, polyphosphate compositions containing calcium as a cationcontain at least 25 wt. % calcium. For example, in one embodiment, thepolyphosphate compositions containing calcium as a cation contain 7-25wt. % calcium. By way of further example, in one embodiment, thepolyphosphate compositions containing calcium as a cation contain 7-35wt. % calcium. In each of these embodiments, the calcium polyphosphatemay optionally contain magnesium and one or more of the other nutrientions described herein, or yet other compositions that may contribute tothe nutritional, material or handling characteristics of thepolyphosphate composition as a fertilizer.

Calcium polyphosphate fertilizers compositions of the present inventionmay optionally contain other components that contribute to thenutritional, material handling, or other characteristics of thefertilizer. For example, the calcium micronutrient fertilizer maycontain a water-soluble N-P-K macronutrient fertilizer that has beenblended or otherwise combined with the calcium polyphosphatecomposition. By way of further example, the calcium polyphosphatefertilizer may contain water-soluble or even water-insoluble nutrientcompounds that has been blended or otherwise combined with the calciumpolyphosphate composition. By way of further example, the calciumpolyphosphate fertilizer may contain organic materials like plantresidues that have been blended or otherwise combined with the calciumpolyphosphate composition to improve the material handlingcharacteristics of calcium polyphosphate fertilizer.

Calcium polyphosphate compositions may be prepared by combining acalcium source material, phosphoric acid and, optionally, one or moreadditional materials to form a reaction mixture and reacting thecomponents of the mixture to form the calcium polyphosphate. Thepolyphosphate is neutralized with calcium oxide or carbonate. Theoptional additional materials include, for example, magnesium and one ormore of the other nutrient ions described herein. The calcium sourcematerial may be any source of calcium that is compatible with thepolymerization process of the present invention. Such sources include,for example, calcium oxide, calcium carbonate, limestone, rock phosphate(apatite), calcium sulfate and calcium chloride.

Magnesium Polyphosphate Compositions

In one embodiment, the polyphosphate composition of the presentinvention comprises magnesium as a cation. In general, polyphosphatecompositions containing magnesium as a cation contain at least 7 wt. %magnesium. Typically, polyphosphate compositions containing magnesium asa cation contain at least 10 wt. % magnesium. In certain embodiments,polyphosphate compositions containing magnesium as a cation contain atleast 13 wt. % magnesium. In certain embodiments, polyphosphatecompositions containing magnesium as a cation contain at least 15 wt. %magnesium. In other embodiments, polyphosphate compositions containingmagnesium as a cation contain at least 20 wt. % magnesium. In otherembodiments, polyphosphate compositions containing magnesium as a cationcontain at least 25 wt. % magnesium. In each of these embodiments, themagnesium polyphosphate may optionally contain calcium and one or moreof the other nutrient ions described herein, or yet other compositionsthat may contribute to the nutritional, material or handlingcharacteristics of the polyphosphate composition as a fertilizer.

Magnesium polyphosphate fertilizers of the present invention mayoptionally contain other components that contribute to the nutritional,material handling, or other characteristics of the polyphosphatecomposition. For example, the magnesium micronutrient composition maycontain a water-soluble N-P-K macronutrient fertilizer that has beenblended or otherwise combined with the magnesium polyphosphatecomposition. By way of further example, the magnesium polyphosphatecomposition may contain water-soluble or even water-insoluble nutrientcompounds that has been blended or otherwise combined with the magnesiumpolyphosphate composition. By way of further example, the magnesiumpolyphosphate composition may contain organic materials like plantresidues that have been blended or otherwise combined with the magnesiumpolyphosphate composition to improve the material handlingcharacteristics of the composition.

Magnesium polyphosphate compositions may be prepared by combining amagnesium source material, phosphoric acid and, optionally, one or moreadditional materials to form a reaction mixture and reacting thecomponents of the mixture to form the magnesium polyphosphate. Themagnesium polyphosphate is neutralized with a basic magnesium sourcethat may include magnesium oxide and magnesium carbonate. The optionaladditional materials include, for example, calcium and one or more ofthe other nutrient ions described herein. The magnesium source materialmay be any source of magnesium that is compatible with thepolymerization process of the present invention. Such sources include,for example, magnesium oxide, magnesium carbonate, magnesite, magnesiumsulfate, and magnesium chloride.

Polyphosphate Fertilizers Containing Two Alkaline Earth Metal Ions

As noted, the polyphosphate may contain one or more alkaline earth metaland one or more nutrient ions. In general fertilizers that contain twoalkaline earth metals contain at least 7 wt. % alkaline earth metals,more typically at least 10 wt. % of alkaline earth metals. Additionally,the alkaline earth metals may be present in any of the concentrationsrecited herein in connection with the calcium polyphosphate fertilizersand magnesium polyphosphate fertilizers. For example, the fertilizer maycontain 7-35 wt. % calcium and/or 7-35 wt. % magnesium. By way offurther example, the fertilizer may contain 7-25 wt. % calcium and/or7-25 wt. % magnesium. In addition, the fertilizer may optionallycomprise one or more of the nutrient ions such as one or more ofpotassium, ammonium, sodium, zinc, iron, manganese, copper, boron,molybdenum, selenium, sulfur, iodine and cobalt.

For certain applications, it is preferred that the alkaline earth metalpolyphosphate contains a combination of nutrient ions. In one suchembodiment, the alkaline earth metals polyphosphate contains potassiumas nutrient ion. For example, in one such embodiment, the potassiumconstitutes at least 0.01 wt. % of the alkaline earth metalspolyphosphate composition. By way of further example, in one suchembodiment, the potassium constitutes at least 2 wt. % of the alkalineearth metals polyphosphate composition. By way of further example, inone such embodiment, the potassium constitutes at least 10 wt. % of thealkaline earth metals polyphosphate composition. By way of furtherexample, in one such embodiment, the potassium constitutes at least 20wt. % of the alkaline earth metals polyphosphate composition.

For other applications it is preferred that the micronutrient metalpolyphosphate contain ammonium as nutrient ion. For example, in one suchembodiment, the ammonium constitutes at least 0.01 wt. % of the alkalineearth metal polyphosphate composition. By way of further example, in onesuch embodiment, the ammonium constitutes at least 4 wt. % of thealkaline earth metal polyphosphate composition. By way of furtherexample, in one such embodiment, the ammonium constitutes at least 10wt. % of the alkaline earth metal polyphosphate composition. By way offurther example, in one such embodiment, the ammonium constitutes 4-15wt. % of the alkaline earth metal polyphosphate composition.

For other applications it is preferred that the alkaline earth metalpolyphosphate contains zinc as nutrient ion. For example, in one suchembodiment, the zinc constitutes at least 0.01 wt. % of the alkalineearth metal polyphosphate composition. By way of further example, in onesuch embodiment, the zinc constitutes less than 9 wt. % of the alkalineearth metal polyphosphate composition. By way of further example, in onesuch embodiment, the zinc constitutes less than 5 wt. % of the alkalineearth metal polyphosphate composition. By way of further example, in onesuch embodiment, the zinc constitutes less than 2 wt. % of the alkalineearth metal polyphosphate composition.

For other applications it is preferred that the alkaline earth metalpolyphosphate contains iron as nutrient ion. For example, in one suchembodiment, the iron constitutes at least 0.01 wt. % of the alkalineearth metal polyphosphate composition. By way of further example, in onesuch embodiment, the iron constitutes less than 6 wt. % of the alkalineearth metal polyphosphate composition. By way of further example, in onesuch embodiment, the iron constitutes less than 3 wt. % of the alkalineearth metal polyphosphate composition. By way of further example, in onesuch embodiment, the iron constitutes less than 1 wt. % of the alkalineearth metal polyphosphate composition.

For other applications it is preferred that the alkaline earth metalpolyphosphate contains manganese as nutrient ion. For example, in onesuch embodiment, the manganese constitutes at least 0.01 wt. % of thealkaline earth metal polyphosphate composition. By way of furtherexample, in one such embodiment, the manganese constitutes less than 5wt. % of the alkaline earth metal polyphosphate composition. By way offurther example, in one such embodiment, the manganese constitutes lessthan 2 wt. % of the alkaline earth metal polyphosphate composition. Byway of further example, in one such embodiment, the manganeseconstitutes less than 1 wt. % of the alkaline earth metal polyphosphatecomposition.

For other applications it is preferred that the alkaline earth metalpolyphosphate contains copper as nutrient ion. For example, in one suchembodiment, the copper constitutes at least 0.01 wt. % of the alkalineearth metal polyphosphate composition. By way of further example, in onesuch embodiment, the copper constitutes less than 5 wt. % of thealkaline earth metal polyphosphate composition. By way of furtherexample, in one such embodiment, the copper constitutes less than 2 wt.% of the alkaline earth metal polyphosphate composition. By way offurther example, in one such embodiment, the copper constitutes lessthan 1 wt. % of the alkaline earth metal polyphosphate composition.

For other applications it is preferred that the alkaline earth metalpolyphosphate contains boron as nutrient ion. For example, in one suchembodiment, the boron constitutes at least 0.01 wt. % of the alkalineearth metal polyphosphate composition. By way of further example, in onesuch embodiment, the boron constitutes less than 5 wt. % of the alkalineearth metal polyphosphate composition. By way of further example, in onesuch embodiment, the boron constitutes less than 2 wt. % of the alkalineearth metal polyphosphate composition. By way of further example, in onesuch embodiment, the boron constitutes less than 1 wt. % of the alkalineearth metal polyphosphate composition.

For other applications it is preferred that the alkaline earth metalpolyphosphate contains selenium as nutrient ion. For example, in onesuch embodiment, the selenium constitutes at least 0.01 wt. % of thealkaline earth metal polyphosphate composition. By way of furtherexample, in one such embodiment, the selenium constitutes less than 5wt. % of the alkaline earth metal polyphosphate composition. By way offurther example, in one such embodiment, the selenium constitutes lessthan 2 wt. % of the alkaline earth metal polyphosphate composition. Byway of further example, in one such embodiment, the selenium constitutesless than 1 wt. % of the alkaline earth metal polyphosphate composition

For other applications it is preferred that the alkaline earth metalpolyphosphate contain one or more of the nutrient ions disclosed herein.For example, in one embodiment the alkaline earth metal polyphosphatemay contain less than 5 wt. % zinc and less than 2 wt. % boron. By wayof further example, in one embodiment the micronutrient metalpolyphosphate may contain less than 3 wt. % zinc and less than 2 wt. %boron. By way of further example, in one embodiment the micronutrientmetal polyphosphate may contain less than 2 wt. % zinc and less than 0.2wt. % boron.

For other applications it is preferred that the alkaline earth metalpolyphosphate contain potassium, zinc, iron and manganese as nutrients.For example, in one such embodiment, the potassium, zinc, iron andmanganese, in combination, constitute less than 20 wt. % of the alkalineearth metal polyphosphate composition. By way of further example, in onesuch embodiment, the potassium, zinc, iron and manganese, incombination, constitute less than 10 wt. % of the alkaline earth metalpolyphosphate composition. By way of further example, in one suchembodiment, the potassium, zinc, iron and manganese, in combination,constitute less than 5 wt. % of the alkaline earth metal polyphosphatecomposition.

Methods of Producing Polyphosphate Compositions

In an illustrative embodiment, the polyphosphate compositions areproduced by heating alkaline earth metal containing compounds such asoxides, carbonates, hydroxides, phosphates, sulfates or combinationsthereof, with phosphoric acid, and optionally nutrient compounds andoptionally water. In an embodiment, heating alkaline earth metalcontaining compounds such as metal oxides, metal carbonates, orcombinations thereof, with phosphoric acid, and optionally water,produces polyphosphates. In an alternative embodiment, the polyphosphatecompositions are produced by pre-heating phosphoric acid and optionallywater to between about 60° C. and 140° C., or to between 60° C. and 200°C. and then combining alkaline earth metal containing compounds such asoxides, carbonates, hydroxides or combinations thereof and optionallynutrient compounds. In another alternative embodiment, the polyphosphatecompositions are produced by heating alkaline earth metal containingcompounds such as oxides, carbonates, hydroxides or combinationsthereof, with phosphoric acid, and optionally water then addingoptionally nutrient compounds and continuing the heating. In anembodiment, the polymerization step does not include a condensing agentsuch as urea. In an embodiment the heating is not continued till thestage when the polyphosphate becomes solid. In this embodiment, heatingis done only till the stage that the polyphosphate remains a liquid.

After the alkaline earth metal compound is added to the phosphoric acidand optionally water, and optionally sulfuric acid, boric acid, borax,molybdic acid or selenic acid or a salt thereof, the mixture may beheated to between about 70° C. and about 160° C., alternatively betweenabout 80° C. and about 120° C., alternatively between about 80° C. andabout 200° C., alternatively to about 105° C., alternatively to about110° C. Then, the nutrient ion compound and optionally sulfuric acid,boric acid, borax, molybdic acid or selenic acid or a salt thereof maybe added to the mixture of alkaline earth metal compound and phosphoricacid. Contemporaneously with the addition of nutrient ion compound,water is preferably added to the mixture. The mixture of the alkalineearth metal compound, phosphoric acid, optionally nutrient ion compound,and water is preferably heated to between about 70° C. and about 160°C., alternatively between about 80° C. and about 120° C., alternativelybetween about 80° C. and about 200° C., alternatively to about 105° C.,alternatively to about 110° C., and polymerization occurs.

Preferably, during the polymerization stage, for any alkaline earthmetal ion M²⁺, the molar ratio of phosphorous to metal is greater thanabout 1.5:1. Thus, for producing a calcium polyphosphate, the molarratio of phosphorous to calcium taken for polymerization is more than2:1, preferably about 2.2:1, or preferably about 2.5:1, or preferablyabout 3:1. Alternately, for producing a calcium-magnesium polyphosphate,the molar ratio of phosphorous to calcium and magnesium (incombination), taken for polymerization is more than 2:1, preferablyabout 2.7:1. Alternately, for producing a calcium-magnesiumpolyphosphate, the molar ratio of phosphorous to calcium and magnesium(in combination), taken for polymerization is more than 2:1, preferablyabout 3:1

In an alternative embodiment, for any optional nutrient metal ionM^(n+), where n+ is the valance of the metal ion, excess phosphoric acidhas to be taken where the molar ratio of phosphorous to metal is greaterthan about n:1. For example, if the metal ion has a valence of +3, themolar ratio of phosphorous to the metal is greater than 3:1 (e.g., 5moles or more of phosphorous for every mole of metal).

The polymerization step may be terminated when the product is soluble inabout two weight percent citric acid or 0.1 normal hydrochloric acid.Without wishing to be bound by the theory, the product is preferablyheated until just before it becomes insoluble in 0.1 wt. % citric acidor 0.01 normal hydrochloric acid, as over-polymerization may causeinsolubilization in acid and reduce the availability of the nutrients toplants.

The polyphosphate composition product may be poured out of the reactorand cooled. When the product temperature reaches below about 90° C.,water may be added to increase the product's fluidity; additionally, thepolyphosphate composition product may be stirred to further enhanceand/or maintain fluidity. The polyphosphate composition product may alsobe neutralized with a neutralizing base, dried and ground to a powder.

Preferable neutralizing bases include magnesium oxides, magnesiumcarbonates, calcium oxides, calcium carbonates, ammonium hydroxides,ammonium carbonates, sodium hydroxides, sodium carbonates, potassiumhydroxides, potassium carbonates and combinations thereof. Bases aremixed with water prior to their use for neutralizing the polyphosphate.Without wishing to be bound by the theory, addition of water to the basereduces lumping of the neutralized polyphosphate. Preferably, thepolyphosphate composition product is ground to an average particle sizeof less than about 200 mesh, alternatively less than about 150 mesh,alternatively less than about 100 mesh, alternatively less than about 80mesh.

Utilization of Polyphosphate Compositions

The powdered polyphosphate composition product may be added to soilcontaining at least one plant to be fertilized. Alternatively, thepowdered polyphosphate composition product may be added to soil, whichwill receive at least one plant to be fertilized. Without wishing to bebound by the theory, root systems of the plants will release acids toabsorb nutrients from the soil. Accordingly, as the root system of theplants require nutrients they release acids which dissolves the powderedpolyphosphate composition product and provides nourishment to the rootsystem and plant.

The polyphosphate compositions may be mixed with various additivesbefore being added to the soil. Suitable additives include otherfertilizers, pesticides, agrichemicals, bentonite, and attapulgite.Non-limiting examples of other fertilizers include urea, diammoniumphosphate and muriate of potash. Non-limiting examples of otherpesticides include 2-4D, parathion, malation, and s-triazines.Non-limiting examples of other additives and agrichemicals includemanure, gypsum, dolomite, and plant growth hormones.

Alternatively, the polyphosphate compositions may be used as a coatingfor granules of the above-listed other fertilizers, granules of chinaclay, bentonite, and attapulgite. Further, the polyphosphatecompositions may be coated on seeds including soybean, corn and wheat.Still further, the polyphosphate compositions may be suspended, andadded to the soil as a suspension. Furthermore, the polyphosphatecompositions may be granulated alone or in combination with china clay,bentonite, attapulgite, or other fertilizers.

Another optional use of the polyphosphate compositions disclosed hereinis as an animal feed supplement. The polyphosphate composition may bemixed with animal feeds such as grain

Having described the invention in detail, it will be apparent thatmodifications and variations are possible without departing the scope ofthe invention defined in the appended claims. The following non-limitingexamples are provided to further illustrate the present invention andthose of skill in the art should, in light of the present disclosure,appreciate that many changes can be made in the specific embodimentsthat are disclosed and still obtain a like or similar result withoutdeparting from the spirit and scope of the invention.

EXAMPLES

The following methods were used to characterize the materials in theexamples below:

Total cation content: 50 milligrams of sample was dissolved in 3milliliters of concentrated sulphuric acid by heating for a few minutes.The solution was diluted and filtered. Cations in solution were analysedby atomic absorption spectroscopy.

Total phosphorus content: 50 milligrams of sample was fused with sodiumhydroxide in a nickel crucible and taken into solution with water.Phosphorus was determined by the molybdenum blue color method. (SoilChemical Analysis, ML Jackson, 1973, Prentice Hall, New Delhi).

Number Average Chain Length: The titrimetric method reported by VanWazer was followed for the determination of number average chain lengthexcluding ortho using the equation: [{2(total P−orthophosphateP)}/{endgroup P−orthophosphate P}] (Van Wazer, J. R. 1966. Phosphorusand its compounds, Vol. 1. Interscience, New York, N.Y.; Ray S K,Chandra P K, Varadachari C and Ghosh K (1998)). For removingmicronutrient metal cation interferences prior to titrimetricdetermination of polyphosphate chain length, the sample was dissolved in0.1N HCl and stirred with a cation exchange resin in H-form. Thesupernatant solution which was free of cations (except hydrogen) wastitrated for polyphosphate chain length by the method of Van Wazer J. R.1966 referred above).

For solubilities, mesh size of less than 150 mesh was used.

Water solubility: 50 milligrams of sample was placed in a conical flaskand 50 milliliters of water was added to it. This was placed in a rotaryshaker for 30 minutes, then filtered washed and made to volume. Cationsin solution were analysed by atomic absorption spectroscopy. Amount ofcation solubilized was expressed as a percentage of total cationdetermined as described above.

0.1N HCl solubility: Solubility of the samples in 0.1N HCl wasdetermined as described above for citrate solubility.

Citrate solubility: 25 milligrams of samples was placed in a conicalflask and 50 milliliters of 0.1% citric acid was added to it. It wasplaced in a rotary shaker for 20 minutes. It was then filtered washedand made to volume. Cations in solution were determined as described inthe paragraph above. Solubilities in citrate are expressed as apercentage of that dissolved by 0.1 N HCl.

Citrate solubility: 25 milligrams of samples was placed in a conicalflask and 50 milliliters of 0.2% citric acid was added to it. It wasplaced in a rotary shaker for 20 minutes. It was then filtered washedand made to volume. Cations in solution were determined as described inthe paragraph above. Solubilities in citrate are expressed as apercentage of that dissolved by 0.1 N HCl.

EDTA solubility: Solubility of the samples in 0.005 M EDTA wasdetermined as described above for citrate solubility. Solubilities incitrate are expressed as a percentage of that dissolved by 0.1 N HCl.

0.01N HCl solubility: Solubility of the samples in 0.01N HCl wasdetermined as described above for citrate solubility. Solubilities incitrate are expressed as a percentage of that dissolved by 0.1 N HCl.

pH: pH of the fertilizers was recorded on a pH meter in a stirredsuspension containing 1 gram of fertilizer powder in 10 milliliterswater.

X-ray diffraction: XRD of the powdered sample was recorded in a X-raydiffractometer using Cu K_(a) radiation at a scan rate of 2° 2 theta perminute.

Example 1 Polyphosphate Fertilizer with Calcium Equivalent RatioCa:P=0.59:1

The fertilizer of this example one was produced from phosphoric acid andcalcium carbonate. Commercial grade phosphoric acid (58.4% P₂0₅), 66.3grams, was placed in a beaker. In another beaker 50 milliliters of waterwas taken and 25.06 grams calcium carbonate was added to it to form aslurry. This slurry was added to the phosphoric acid with stirring. Itwas then heated in an oil bath for 10 minutes till the temperature ofthe liquid reached 70° C. At this stage the liquid became thick. Afurther 30 milliliters of water was added. It was heated for another 20minutes till the liquid temperature reached 103° C.

The sample was removed from the oil bath and allowed to cool to about80° C. Then 14 grams of calcium oxide was suspended in 100 millilitersof water and added to the phosphate liquid with stirring. At this stagea white suspension was formed and its pH was around 5.0. The product waspoured in a drying dish and dried in an oven at 75° C. After it was dry,the sample was ground and sieved through a 150 mesh sieve.

On analysis, the product showed 19.12 weight percent phosphorus and 22weight percent calcium. The ratio of moles of P:Ca was 1.1:1. The pH ofa 10% suspension in water was 5.5. The number average chain length ofthe excluding orthophosphate was 4.9 and the number average chain lengthincluding ortho was 1.34. The orthophosphate content was 45 wt %.Solubility of calcium from this product in water was 1.1% of the totalcalcium. In 0.1 weight percent citric acid 97% of the total calciumdissolved. In 0.01 N hydrochloric acid 91% of the total calciumdissolved. In 0.005M EDTA, 99% of the total calcium dissolved. XRD peaksof this product is shown in Table 1. NMR peaks of this product are at60.296, 29.824, −0.684, −31.248, −61.673 ppm.

Example 2 Polyphosphate Fertilizer with Magnesium Equivalent RatioMg:P=0.72:1

The fertilizer of this example two was produced from phosphoric acid,and magnesium oxide. Commercial grade phosphoric acid (58.4% P₂0₅), 68.5grams, was placed in a beaker. Then 10.3 grams magnesium oxide wassuspended in 50 milliliters of water and the suspension was added to thephosphoric acid with stirring. It was then heated in an oil bath for 30minutes till the temperature of the liquid reached 115° C. Afterremoving the sample it was allowed to cool to about 80° C. It was thenneutralized with a suspension of magnesium oxide in water (14.5 gramsMgO in 20 milliliters water) which was added in a stream with continuousstirring. At this stage a white suspension was formed. The product waspoured in a drying dish and dried in an oven at 75° C. After it was dry,the sample was ground in a mortar. It was sieved through a 150 meshsieve.

On analysis, the product showed 19 weight percent phosphorus and 16.1weight percent magnesium. The ratio of moles of P:Mg was 0.93:1. Thenumber average chain length excluding orthophosphate was 4.5 and thenumber average chain length including orthophosphate was 1.29. Theorthophosphate content was 24.6 wt %. The pH of a 10% suspension inwater was 6.3. Solubility of this product in water was 1.4% of the totalmagnesium. In 0.1 weight percent citric acid 98% of the total magnesiumdissolved. In 0.01 N hydrochloric acid 97% of the total magnesiumdissolved and in 0.005M EDTA, 98% of the total dissolved magnesium wassoluble. XRD peaks of this product is shown in Table 1. NMR peaks ofthis product are at 58.169, 28.803, 26.496, 23.078, −0.593, −6.213,−30.075, −35.810 ppm.

Example 3 Polyphosphate Fertilizer with Calcium and Zinc EquivalentRatio Ca:P=0.58:1

The fertilizer of this example two was produced from phosphoric acid,calcium carbonate and zinc oxide. Commercial grade phosphoric acid(58.4% P₂0₅), 71.6 grams, was placed in a beaker. Then 25.06 gramscalcium carbonate and 1.61 grams zinc oxide was suspended in 50milliliters of water and the suspension was added to the phosphoric acidwith stirring. It was then heated in an oil bath for 45 minutes till thetemperature of the liquid reached 105° C. The beaker was removed fromthe heating unit and allowed to cool to about 70° C. Then a suspensionof calcium oxide in water (14.5 grams CaO in 30 milliliters water) wasadded in a stream with continuous stirring. At this stage a whitesuspension was formed. The product was poured in a drying dish and driedin an oven at 75° C. After it was dry, the sample was ground by hand ina mortar. It was sieved through a 150 mesh sieve.

On analysis, the product showed 18.56 weight percent phosphorus, 20.7weight percent calcium and 1.3 weight percent zinc. The ratio of molesof P:Ca:Zn was 30:26:1. The ratio of moles of P:Ca was 1.16:1. The pH ofa 10% suspension in water was 6.5. Solubility of calcium from thisproduct in water was 0.9% of the total calcium and 1% of totalmagnesium. In 0.1 weight percent citric acid 99% of the total calciumand 97% of the total zinc dissolved. In 0.01 N hydrochloric acid 99% ofthe total calcium and 98% of the total zinc dissolved. In 0.005M EDTA,98% of the total calcium and 97% of total zinc dissolved. XRD peaks ofthis product is shown in Table 1. NMR of this product shows peaks at60.165, 29.703, −0.709, −31.241, −61.572 ppm.

Example 4 Polyphosphate Fertilizer with Calcium, and Rock PhosphateEquivalent Ratio Ca:P=0.57:1

The fertilizer of this example was produced from phosphoric acid,calcium carbonate and rock phosphate. Commercial grade phosphoric acid(58.5% P₂0₅), 17.1 grams, was placed in a beaker. Then 25 grams rockphosphate was suspended in 50 milliliters of water and the suspensionwas added to the phosphoric acid with stirring. It was then heated in anoil bath till the temperature of the liquid reached 105° C. Then asuspension of 4.6 grams of calcium carbonate in 20 milliliters water wasadded to it. The beaker was heated again for 15 minutes till the liquidtemperature reached 105° C. whereupon it was removed from the oil bath.When the liquid had cooled to about 75° C., a suspension of calciumoxide in water (7 g CaO in 15 milliliters water) was added in a streamwith continuous stirring. The product was poured in a drying dish anddried in an oven at 75° C. After it was dry, the sample was ground byhand in a mortar. It was sieved through a 150 mesh sieve.

On analysis, the product showed mainly 19.12 weight percent phosphorusand 21 weight percent calcium. The ratio of moles of P:Ca was 1.2:1. ThepH of a 10% suspension in water was 7.2. Solubility of calcium from thisproduct in water was 0.1% of the total calcium. In 0.1 weight percentcitric acid 91% of the total calcium dissolved. In 0.01 N hydrochloricacid 88% of the total calcium dissolved. In 0.005M EDTA, 95% of thetotal calcium dissolved.

Example 5 Polyphosphate Fertilizer with Calcium and Magnesium EquivalentRatio (Ca+Mg):P=0.54:1

The fertilizer of this example was produced from phosphoric acid,calcium carbonate and magnesium oxide. Commercial grade phosphoric acid(58.4% P₂0₅), 83 grams, was placed in a beaker. Then 25.06 grams calciumcarbonate and 8.1 grams magnesium oxide was suspended in 80 millilitersof water and the suspension was added to the phosphoric acid withstirring. Exothermic reaction occurs and the liquid temperature israised to 70° C. It was then heated in an oil bath for 40 minutes tillthe temperature of the liquid reached 107° C. The beaker was removedfrom the heating unit and when the liquid had cooled to about 80° C., asuspension of calcium oxide in water (10.5 g CaO in 20 milliliterswater) was added in a stream with continuous stirring. The product waspoured in a drying dish and dried in an oven at 75° C. After it was dry,the sample was ground in a mortar. It was sieved through a 150 meshsieve.

On analysis, the product showed 19.85 weight percent phosphorus, 13.1weight percent calcium and 4.6 weight percent magnesium. The ratio ofmoles of P:Ca:Mg was 3.4:1.7:1. The ratio of moles of P:(Ca+Mg) was1.24:1. The pH of a 10% suspension in water was 4.9. Solubility ofcalcium from this product in water was 0.6% of the total calcium and4.7% of total magnesium. In 0.1 weight percent citric acid 98% of thetotal calcium and 98% of the total magnesium dissolved. In 0.01 Nhydrochloric acid 97% of the total calcium and 98% of total magnesiumdissolved. In 0.005M EDTA, 98% of the total calcium and magnesiumdissolved. XRD for this product showed peaks at 6.8, 5.96, 5.37, 5.01,4.7, 4.61, 4.5, 4.15, 3.7, 3.66, 3.58, 3.47, 3.39, 3.35, 3.19, 3.13,3.09, 3.05, 2.96, 2.94, 2.82, 2.76, 2.73, 2.59, 2.53, 2.5, 2.43, 2.41,2.39, 2.37, 2.34, 2.25, 2.2, 2.18, 2.16, 2.14, 2.12, 2.09, 2.08, 2.03,1.99, 1.93, 1.91, 1.85, 1.8, 1.76, 1.72, 1.68, 1.64, 1.59 and 1.57 Å(Table 1).

Example 6 Polyphosphate Fertilizer with Calcium and Magnesium EquivalentRatio (Ca+Mg):P=0.66:1

The fertilizer of this example two was produced from phosphoric acid,calcium carbonate and magnesium oxide. Commercial grade phosphoric acid(58.4% P₂0₅), 83 grams, was placed in a beaker. Then 40 grams calciumcarbonate and 8.1 grams magnesium oxide was suspended in 80 millilitersof water and the suspension was added to the phosphoric acid withstirring. Exothermic reaction occurs and the liquid temperature israised to 70° C. It was then heated in an oil bath for 30 minutes tillthe temperature of the liquid reached 103° C. The beaker was removedfrom the heating unit and when the liquid had cooled to about 80° C., asuspension of calcium oxide in water (5 g CaO in 20 milliliters water)was added in a stream with continuous stirring. The product was pouredin a drying dish and dried in an oven at 75° C. After it was dry, thesample was ground in a mortar. It was sieved through a 150 mesh sieve.

On analysis, the product showed 19.46 weight percent phosphorus, 17.6weight percent calcium and 4.5 weight percent magnesium. The ratio ofmoles of P:Ca:Mg was 3.4:2.4:1. The ratio of moles of P:(Ca+Mg) was1.01:1. The pH of a 10% suspension in water was 4.9. The number averagechain length excluding orthophosphate was 4.5 and the number averagechain length including orthophosphate was 1.83, The orthophosphatecontent was 20.5 wt % Solubility of calcium from this product in waterwas 0.4% of the total calcium and 4.9% of total magnesium. In 0.1 weightpercent citric acid 95% of the total calcium and 96% of the totalmagnesium dissolved. In 0.01 N hydrochloric acid 96% of the totalcalcium and 98% of total magnesium dissolved. In 0.005M EDTA, 96% of thetotal calcium and 98% of total magnesium dissolved.

Example 7 Polyphosphate Fertilizer with Calcium and Potassium EquivalentRatio Ca:P=0.61:1

The fertilizer of this example three was produced from phosphoric acid,calcium carbonate and potassium chloride. Commercial grade phosphoricacid (58.4% P₂0₅), 99.5 grams, was placed in a beaker. Then 25.06 gramscalcium carbonate and 10.58 grams magnesium oxide was suspended in 50milliliters of water and the suspension was added to the phosphoric acidwith stirring. It was then heated in an oil bath for 40 minutes till thetemperature of the liquid reached 132° C. The beaker was removed fromthe heating unit and allowed to cool to about 80° C. Then a suspensionof calcium oxide in water (28 grams CaO in 30 milliliters water) wasadded in a stream with continuous stirring. At this stage a whitesuspension was formed. The product was poured in a drying dish and driedin an oven at 75° C. After it was dry, the sample was ground by hand ina mortar. It was sieved through a 150 mesh sieve.

On analysis, the product showed 18.4 weight percent phosphorus, 21.7weight percent calcium and 4 weight percent potassium. The ratio ofmoles of P:Ca:K was 5.8:5.3:1. The pH of a 10% suspension in water was5.2. In 0.1 weight percent citric acid 97% of the total calcium and 96%of the total potassium dissolved. In 0.01 N hydrochloric acid 95% of thetotal calcium and 97% of the total potassium dissolved. In 0.005M EDTA,94% of the total calcium and 96% of the total potassium dissolved. XRDpeaks of this product is shown in Table 1. NMR of this product showspeaks at 57.461, 28.396, −0.513, −29.452, −58.652 ppm.

Example 8 Polyphosphate Fertilizer with Calcium, Magnesium and BoronEquivalent Ratio (Ca+Mg):P=0.67:1

The fertilizer of this example was produced from phosphoric acid,magnesium oxide, boric acid and sodium carbonate. Commercial gradephosphoric acid (58.4% P₂0₅), 83 grams, was placed in a beaker. Then 40grams calcium carbonate and 8.1 grams magnesium oxide was suspended in80 milliliters of water and the suspension was added to the phosphoricacid with stirring. 6 grams sodium carbonate was then dissolved in aminimum volume of water and 10 grams of boric acid (17.3% B) was addedto it. It was heated till the boric acid dissolved. This solution wasadded to the phosphoric acid solution containing calcium and magnesium.It was then heated in an oil bath for 30 minutes till the temperature ofthe liquid reached 107° C. The beaker was removed from the heating unitand when the liquid had cooled to about 80° C., a suspension of calciumoxide in water (5 g CaO in 20 milliliters water) was added in a streamwith continuous stirring. The product was poured in a drying dish anddried in an oven at 75° C. After it was dry, the sample was ground in amortar. It was sieved through a 150 mesh sieve.

On analysis, the product showed 18.7 weight percent phosphorus, 17.3weight percent calcium, 4.3 weight percent magnesium and 1.48 weightpercent boron. The ratio of moles of P:Ca:B was 4.4:3.1:1. The pH of a10% suspension in water was 5.2. In 0.1 weight percent citric acid 98%of the total calcium dissolved. In 0.01 N hydrochloric acid 97% of thetotal calcium dissolved. In 0.005M EDTA, 99% of the total calciumdissolved.

Example 9 Polyphosphate Fertilizer with Calcium (Using TricalciumPhosphate) Equivalent Ratio Ca:P=0.7:1

The fertilizer of this example was produced from phosphoric acid,tricalcium phosphate and calcium oxide. Commercial grade phosphoric acid(58.4% P₂0₅), 53.9 grams, was placed in a beaker. Then 25 gramstricalcium phosphate suspended in 40 milliliters of water and was addedto the phosphoric acid with stirring. The mixture was heated in an oilbath for 30 minutes till the temperature of the liquid reached 107° C.The beaker was removed from the heating unit and when the liquid hadcooled to about 80° C., a suspension of calcium oxide in water (20 g CaOin 40 milliliters water) was added in a stream with continuous stirring.The product was poured in a drying dish and dried in an oven at 75° C.After it was dry, the sample was ground in a mortar. It was sievedthrough a 100 mesh sieve.

On analysis, the product showed 26.7 weight percent phosphorus and 24.7weight percent calcium. The ratio of moles of P:Ca was 0.96:1. The pH ofa 10% suspension in water was 4.5. Solubility of calcium from thisproduct in water was 1.9% of the amount of calcium that dissolves in 0.1N HCl in 20 minutes. Solubility of calcium in 0.1 weight percent citricacid was 83% of the calcium that dissolves in 0.1 N HCl in 20 minutes.Solubility of calcium in 0.2 wt % citric acid was 96% of calcium thatdissolved in 0.1N HCl in 20 minutes. Solubility of calcium in 0.01 Nhydrochloric acid and in 0.005M EDTA was 82% and 94% respectively, ofthe amount of calcium that dissolves in 0.1 N HCl in 20 minutes. Thenumber average chain length of the product excluding orthophosphate was2.93 and the number average chain length including ortho was 1.4. Theorthophosphate content was 57 wt %. XRD of this sample is shown in Table1.

Example 10 Polyphosphate Fertilizer with Calcium (Using TricalciumPhosphate) Equivalent Ratio Ca:P=0.66:1

The fertilizer of this example one was produced from phosphoric acidtricalcium phosphate and calcium oxide. Commercial grade phosphoric acid(58.4% P₂0₅), 68.6 grams, was placed in a beaker. In another beaker 50milliliters of water was taken and 25 grams tricalcium phosphate wasadded to it to form a slurry. This slurry was added to the phosphoricacid with stirring. It was then heated in an oil bath for 25 minutestill the temperature of the liquid reached 109° C.

The sample was removed from the oil bath. Then 35 grams of calcium oxidewas suspended in 60 milliliters of water and added to the reactionmixture with stirring. At this stage a white suspension was formed andits pH was around 3.5. The product was poured in a drying dish and driedin an oven at 70° C. After it was dry, the sample was ground and sievedthrough a 150 mesh sieve.

On analysis, the product showed 24.4 weight percent phosphorus and 31.2weight percent calcium. The ratio of moles of P:Ca was 1.01:1. The pH ofa 10% suspension in water was 3.5. Solubility of calcium from thisproduct in water was 1.8% of the amount of calcium that dissolves in 0.1N HCl in 20 minutes. Solubility of phosphorus from this product in waterwas 9.8% of the total phosphorus in it. Solubility of calcium in 0.2 wt% citric acid was 85% of calcium that dissolved in 0.1N HCl in 20minutes.

Example 11 Polyphosphate Fertilizer with Calcium (Using TricalciumPhosphate) Equivalent Ratio Ca:P=0.66:1

The fertilizer of this example one was produced as described in Example10 from phosphoric acid tricalcium phosphate and calcium oxide. Here, 36grams of commercial grade phosphoric acid (58.4% P₂0₅), was usedtogether with 25 grams tricalcium phosphate. The mixture was heated towas heated 106° C. and neutralized with 14 grams calcium oxide. Theproduct was then ground and sieved through a 150 mesh sieve.

On analysis, the product showed 24.3 weight percent phosphorus and 30.9weight percent calcium. The ratio of moles of P:Ca was 1.02:1. The pH ofa 10% suspension in water was 5.4. Solubility of calcium from thisproduct in water was 1.5% of the amount of calcium that dissolves in0.1N HCl in 20 minutes. Solubility of phosphorus from this product inwater was 9.6% of the total phosphorus in it. Solubility of calcium in0.2 wt % citric acid was 93% of calcium that dissolved in 20 minutes.Solubility of calcium in 0.01 N hydrochloric acid and in 0.005M EDTA was79% and 87% respectively, of the amount of calcium that dissolves in 0.1N HCl in 20 minutes.

Example 12 (Polyphosphate Fertilizer with Calcium (Using TricalciumPhosphate) Equivalent Ratio Ca:P=0.71:1

The fertilizer of this example one was produced as described in Example9 except that the mixture was heated to 110° C. and neutralized with 22grams calcium oxide.

On analysis, the product showed 19.2 weight percent phosphorus and 26.5weight percent calcium. The ratio of moles of P:Ca was 0.94:1. The pH ofa 10% suspension in water was 5. Solubility of calcium from this productin water was 1.1% of the calcium that dissolves in 0.1 N HCl in 20minutes. Solubility of calcium in 0.01 N hydrochloric acid and in 0.005MEDTA was 59% and 71% respectively, of the amount of calcium thatdissolves in 0.1 N HCl in 20 minutes. Solubility of calcium in 0.1 wt %citric acid was 63% of calcium that dissolved in 20 minutes.

Example 13 Polyphosphate Fertilizer with Calcium and MagnesiumEquivalent Ratio (Ca+Mg):P=0.63:1

The fertilizer of this example was produced from phosphoric acid,tricalcium phosphate, magnesium oxide and calcium oxide. Commercialgrade phosphoric acid (58.4% P₂0₅), 72 grams, was placed in a beaker.Then 25 grams tricalcium phosphate and 2.44 grams magnesium oxide wassuspended in 45 milliliters of water and the suspension was added to thephosphoric acid with stirring. It was then heated in an oil bath for 30minutes till the temperature of the liquid reached 109° C. The beakerwas removed from the heating unit and mixed with a suspension of calciumoxide in water (32 g CaO in 50 milliliters water. The product was driedin an oven at 75° C. and ground in a mortar. It was sieved through a 100mesh sieve.

On analysis, the product showed 22 weight percent phosphorus, 24.2weight percent calcium and 1.8 weight percent magnesium. The ratio ofmoles of P:(Ca+Mg) was 1.07:1. The pH of a 10% suspension in water was3.6. Solubility of calcium and magnesium from this product in water was2.5% and 0.3% respectively, of the calcium and magnesium that dissolvedin 0.1N HCl in 20 minutes. Solubility of calcium and magnesium in 0.01 Nhydrochloric acid was 99% and 100% respectively, of the calcium andmagnesium that dissolved in 0.1N HCl in 20 minutes. Solubility in 0.005MEDTA was 100% of the calcium and magnesium of the calcium and magnesiumthat dissolved in 0.1 N HCl in 20 minutes. Solubility of calcium andmagnesium in 0.2 wt % citric acid was 100% of calcium and magnesium thatdissolved in 0.1 N HCl in 20 minutes.

Example 14 Polyphosphate Fertilizer with Rock Phosphate Equivalent RatioCa:P=0.56:1

The fertilizer of this example was produced from phosphoric acid, rockphosphate (apatite) and calcium carbonate. Commercial grade phosphoricacid (58.4% P₂0₅), 59.5 grams, was placed in a beaker. Then 30 gramsrock phosphate was suspended in 35 milliliters of water and thesuspension was added to the phosphoric acid with stirring. It was thenheated in an oil bath for 30 minutes till the temperature of the liquidreached 112° C. The beaker was removed from the heating unit and mixedwith a suspension of calcium carbonate in water (42 g CaO in 140milliliters water. The product was dried in an oven at 75° C. and groundin a mortar.

On analysis, the product showed 24.3 weight percent phosphorus and 25.9weight percent calcium. The ratio of moles of P:(Ca+Mg) was 1.22:1. ThepH of a 10% suspension in water was 4.5. Solubility of calcium from thisproduct in water was 2.8% of the calcium and magnesium that dissolved in0.1N HCl in 20 minutes. Solubility of phosphorus from this product inwater was 12.6% of the total phosphorus in it. Solubility of calcium in0.1 weight percent citric acid was 77% of the total calcium dissolved in20 minutes. Solubility of calcium in 0.2 wt % citric acid was 89% ofcalcium that dissolved in 0.1N HCl in 20 minutes.

Example 15 Polyphosphate Fertilizer with Calcium and MagnesiumEquivalent Ratio (Ca+Mg):P=0.7:1

The fertilizer of this example was produced from phosphoric acid,calcium carbonate and magnesium carbonate. Commercial grade phosphoricacid (58.4% P₂0₅), 95 grams, was placed in a beaker. Then 25 gramscalcium carbonate and 5.27 grams magnesium carbonate was suspended in 70milliliters of water and the suspension was added to the phosphoric acidwith stirring. It was then heated in an oil bath for 20 minutes till thetemperature of the liquid reached 105° C. The beaker was removed fromthe heating unit and mixed with a suspension of calcium carbonate inwater (50 g CaCO₃ in 50 milliliters water. The product was dried in anoven at 70° C. and ground in a mortar. It was sieved through a 150 meshsieve.

On analysis, the product showed 22.6 weight percent phosphorus, 27.7weight percent calcium and 1.8 weight percent magnesium. The ratio ofmoles of P:(Ca+Mg) was 0.95:1. The pH of a 10% suspension in water was4.1. Solubility of calcium and magnesium from this product in water was1.4% and 0.4% of the calcium and magnesium that dissolved in 0.1 N HClin 20 minutes. Solubility of calcium and magnesium from this product in0.01 N HCl was 97% and 99% of the calcium and magnesium that dissolvedin 0.1N HCl in 20 minutes. Solubility of phosphorus from this product inwater was 21% of the total phosphorus. Solubility of calcium andmagnesium from this product in water was 1.4% and 0.4% of the calciumand magnesium that dissolved in 0.1N HCl in 20 minutes. Solubility ofcalcium and magnesium from this product 0.1 weight percent citric acidwas 75.2% and 78.9% of the calcium and magnesium that dissolved in 0.1NHCl in 20 minutes.

Example 16 Polyphosphate Fertilizer with Rock Phosphate and ZincEquivalent Ratio Ca:P=0.6:1

The fertilizer of this example was produced from phosphoric acid, rockphosphate, zinc oxide and calcium oxide. Commercial grade phosphoricacid (58.4% P₂0₅), 78 grams, was placed in a beaker. Then 30 grams rockphosphate and 5 grams zinc oxide was suspended in 50 milliliters ofwater and the suspension was added to the phosphoric acid with stirring.It was then heated in an oil bath for 20 minutes till the temperature ofthe liquid reached 109° C. The beaker was removed from the heating unitand mixed with a suspension of calcium oxide in water (42 g CaO in 70milliliters water). The product was dried in an oven at 70° C. andground in a mortar. It was sieved through a 150 mesh sieve.

On analysis, the product showed 19.6 weight percent phosphorus, 22.8weight percent calcium and 4.6 weight percent zinc. The ratio of molesof P:Ca was 1.1:1. The pH of a 10% suspension in water was 4.9.Solubility of calcium and magnesium from this product in water was 1.7%and 0.7% of the calcium and zinc that dissolved in 0.1N HCl in 20minutes. Solubility of phosphorus from this product in water was 16.6%of the total phosphorus. Solubility of calcium and magnesium from thisproduct in 0.01N HCl was 75% and 100% of the calcium and zinc thatdissolved in 0.1N HCl in 20 minutes. Solubility of calcium and magnesiumfrom this product in 0.1 weight percent citric acid was 75.2% and 84% ofthe calcium and zinc that dissolved in 0.1N HCl in 20 minutes.Solubility of calcium and magnesium from this product in 0.2 weightpercent citric acid was 91% and 94% of the calcium and zinc thatdissolved in 0.1 N HCl in 20 minutes.

Example 17 Polyphosphate Fertilizer with Calcium and Zinc EquivalentRatio Ca:P=0.61:1

The fertilizer of this example was produced from phosphoric acid, zincoxide and calcium carbonate. Commercial grade phosphoric acid (58.4%P₂0₅), 122 grams, was placed in a beaker. Then 25 calcium carbonate and12.5 grams zinc oxide was suspended in 200 milliliters of water and thesuspension was added to the phosphoric acid with stirring. It was thenheated in an oil bath for 15 minutes till the temperature of the liquidreached 107° C. The beaker was removed from the heating unit and mixedwith a suspension of calcium carbonate in water (67 g CaCO₃ in 100milliliters water). The product was dried in an oven at 65° C. andground in a mortar. It was sieved through a 150 mesh sieve.

On analysis, the product showed 22.5 weight percent phosphorus, 26.5weight percent calcium and 7.2 weight percent zinc. The ratio of molesof P:Ca was 1.1:1. The pH of a 10% suspension in water was 4.6.Solubility of calcium and zinc from this product in water was 2.2% and0.4% of the calcium and zinc that dissolved in 0.1 N HCl in 20 minutes.Solubility of calcium and zinc from this product in 0.01 N HCl was 87and 82% of the calcium and zinc that dissolved in 0.1N HCl in 20minutes. Solubility of calcium and zinc from this product in 0.005M EDTAwas 92% and 89% of the calcium and zinc that dissolved in 0.1N HCl in 20minutes. Solubility of calcium and zinc that dissolved from this productin 0.1 weight percent citric acid was 81% and 84% of the calcium andzinc that dissolved in 0.1N HCl in 20 minutes. XRD of this product iosshown in Table 1.

Example 18 Polyphosphate Fertilizer with Calcium and Iron EquivalentRatio Ca:P=0.54:1

The fertilizer of this example was produced from phosphoric acid,tricalcium phosphate, magnetite and calcium carbonate. Commercial gradephosphoric acid (58.4% P₂0₅), 92 grams, was placed in a beaker. Then 25tricalcium phosphate and 7.25 grams magnetite was suspended in 90milliliters of water and the suspension was added to the phosphoric acidwith stirring. It was then heated in an oil bath for 15 minutes till thetemperature of the liquid reached 102° C. The beaker was removed fromthe heating unit and mixed with a suspension of calcium carbonate inwater (62 g CaCO₃ in 100 milliliters water). The product was dried in anoven at 65° C. and ground in a mortar. It was sieved through a 150 meshsieve.

On analysis, the product showed 23.1 weight percent phosphorus, 24.1weight percent calcium and 4 weight percent iron. The ratio of moles ofP:Ca was 1.24:1. The pH of a 10% suspension in water was 3.9. Solubilityof calcium and magnesium from this product in water was 2.4% and 1.4% ofthe calcium and iron that dissolved in 0.1 N HCl in 20 minutes.Solubility of phosphorus from this product in water was 12.5% of thetotal phosphorus. Solubility of calcium from this product in 0.01 N HClwas 77.9% of the calcium that dissolved in 0.1 N HCl in 20 minutes.Solubility of calcium and iron from this product in 0.005M EDTA was 85%and 84% of the calcium and iron that dissolved in 0.1N HCl in 20minutes. Solubility of calcium and iron from this product in 0.1 weightpercent citric acid was 79% and 74% of the calcium and iron thatdissolved in 0.1 N HCl in 20 minutes. Solubility of calcium and ironfrom this product in 0.2 weight percent citric acid was 86% and 81% ofthe calcium and iron that dissolved in 0.1 N HCl in 20 minutes. XRD ofthis product ios shown in Table 1.

Example 19 Polyphosphate Fertilizer with Calcium and ManganeseEquivalent Ratio Ca:P=0.72:1

The fertilizer of this example was produced from phosphoric acid,tricalcium phosphate, manganous oxide and calcium carbonate. Commercialgrade phosphoric acid (58.4% P₂0₅), 82 grams, was placed in a beaker.Then 25 tricalcium phosphate and 8.3 grams manganous oxide was suspendedin 75 milliliters of water and the suspension was added to thephosphoric acid with stirring. It was then heated in an oil bath for 15minutes till the temperature of the liquid reached 102° C. The beakerwas removed from the heating unit and mixed with a suspension of calciumcarbonate in water (50 g CaCO₃ in 125 milliliters water). The productwas dried in an oven at 70° C. and ground in a mortar. It was sievedthrough a 150 mesh sieve.

On analysis, the product showed 18.4 weight percent phosphorus, 25.9weight percent calcium and 4 weight percent manganese. The ratio ofmoles of P:Ca was 0.92:1. The pH of a 10% suspension in water was 6.1.Solubility of calcium and manganese from this product in water was 3.9%and 0.2% of the calcium and manganese that dissolved in 0.1 N HCl in 20minutes. Solubility of phosphorus from this product in water was 19.6%of the total phosphorus. Solubility of calcium and manganese from thisproduct in 0.01 N HCl was 82% and 95% respectively, of the calcium andmanganese that dissolved in 0.1 N HCl in 20 minutes. Solubility ofcalcium and manganese from this product in 0.005M EDTA was 100% and 100%of the calcium and manganese that dissolved in 0.1 N HCl in 20 minutes.Solubility of calcium and manganese from this product in 0.1 weightpercent citric acid was 89% and 94% of the calcium and manganese thatdissolved in 0.1 N HCl in 20 minutes. XRD of this product ios shown inTable 1.

Example 20 Polyphosphate Fertilizer with Calcium and Boron EquivalentRatio Ca:P=0.60:1

The fertilizer of this example was produced from phosphoric acid,tricalcium phosphate, boric acid, sodium carbonate and calciumcarbonate. Commercial grade phosphoric acid (58.4% P₂0₅), 54 grams, wasplaced in a beaker. Then 11.4 grams boric acid and 15.4 grams sodiumcarbonate were suspended in 80 milliliters water and heated to dissolve.Then 25 tricalcium phosphate was suspended in 55 milliliters of waterand the suspension was added to the phosphoric acid with stirring. Itwas then heated in an oil bath for 15 minutes till the temperature ofthe liquid reached 95° C. The solution of neutralized boric acid wasadded to it and heating was continued till the temperature reached 105°C. Heating was discontinued and after the suspension cooled to around90° C., it was mixed with a suspension of calcium carbonate in water (30g CaCO₃ in 100 milliliters water). The product was dried in an oven at80° C. and ground in a mortar. It was sieved through a 150 mesh sieve.

On analysis, the product showed 18 weight percent phosphorus, 21 weightpercent calcium and 1.9 weight percent boron. The ratio of moles of P:Cawas 1.11:1. The pH of a 10% suspension in water was 6.1. Solubility ofcalcium from this product in water was 3.4% of the calcium thatdissolved in 0.1N HCl in 20 minutes. Solubility of calcium and boronfrom this product in 0.01N HCl was 100% and 100% respectively, of thecalcium and boron that dissolved in 0.1 N HCl in 20 minutes. Solubilityof calcium and boron from this product in 0.005M EDTA was 100% and 100%of the calcium and boron that dissolved in 0.1N HCl in 20 minutes.Solubility of calcium and boron from this product in 0.1 weight percentcitric acid was 95% and 98% of the calcium and boron that dissolved in0.1N HCl in 20 minutes. Solubility of calcium and boron from thisproduct in 0.2 weight percent citric acid was 96% and 99% of the calciumand boron that dissolved in 0.1 N HCl in 20 minutes.

Example 21 Polyphosphate Fertilizer with Calcium and Boron EquivalentRatio Ca:P=0.57:1

The fertilizer of this example was produced from phosphoric acid,tricalcium phosphate, borax and calcium carbonate. Commercial gradephosphoric acid (58.4% P₂0₅), 54 grams, was placed in a beaker. Then17.64 grams borax was dissolved in 75 milliliters water and heated todissolve. Then 25 tricalcium phosphate was suspended in 55 millilitersof water and the suspension was added to the phosphoric acid withstirring. It was then heated in an oil bath for 15 minutes till thetemperature of the liquid reached 95° C. The solution of borax was addedto it and heating was continued till the temperature reached 105° C.Heating was discontinued and after the suspension cooled to around 90°C., it was mixed with a suspension of calcium carbonate in water (30 gCaCO₃ in 100 milliliters water). The product was dried in an oven at 80°C. and ground in a mortar. It was sieved through a 150 mesh sieve.

On analysis, the product showed 21.8 weight percent phosphorus, 24.1weight percent calcium and 2.1 weight percent boron. The ratio of molesof P:Ca was 1.17:1. The pH of a 10% suspension in water was 5.0.Solubility of calcium from this product in water was 3.4% of the calciumthat dissolved in 0.1 N HCl in 20 minutes. Solubility of phosphorus fromthis product in water was 21.7% of the total phosphorus. Solubility ofcalcium and boron from this product in 0.01 N HCl was 100% and 100%respectively, of the calcium and boron that dissolved in 0.1N HCl in 20minutes. Solubility of calcium and boron from this product in 0.005MEDTA was 100% and 100% of the calcium and boron that dissolved in 0.1NHCl in 20 minutes. Solubility of calcium and boron from this product in0.1 weight percent citric acid was 97% and 99% of the calcium and boronthat dissolved in 0.1 N HCl in 20 minutes. XRD of this product ios shownin Table 1.

Example 22 Polyphosphate Fertilizer with Calcium and Sulfur EquivalentRatio Ca:P=1.01:1 Also (P+S):Ca=0.97:1

The fertilizer of this example was produced from phosphoric acid,tricalcium phosphate, sulfuric acid and calcium carbonate. Commercialgrade phosphoric acid (58.4% P₂0₅), 36.2 grams, was placed in a beaker.Then 25 tricalcium phosphate was suspended in 50 milliliters of waterand the suspension was added to the phosphoric acid with stirring. Then25 grams of concentrated sulfuric acid was added to it. The suspensionwas heated in an oil bath for 20 minutes till the temperature of theliquid reached 108° C. Heating was discontinued and after the suspensioncooled to around 90° C., it was mixed with a suspension of calciumcarbonate in water (50 g CaCO₃ in 100 milliliters water). The productwas dried in an oven at 80° C. and ground in a mortar. It was sievedthrough a 150 mesh sieve.

On analysis, the product showed 14.6 weight percent phosphorus, 28.5weight percent calcium and 7 weight percent sulfur. The ratio of molesof P:Ca was 0.66:1 and (P+S):Ca was 0.97:1. The pH of a 10% suspensionin water was 4.3. Solubility of calcium from this product in water was4.2% of the calcium that dissolved in 0.1 N HCl in 20 minutes.Solubility of phosphorus from this product in water was 20.4% of thetotal phosphorus. Solubility of calcium and sulfur from this product in0.01 N HCl was 85% and 93% respectively, of the calcium and sulfur thatdissolved in 0.1 N HCl in 20 minutes. Solubility of calcium and sulfurfrom this product in 0.005M EDTA was 95% and 100% of the calcium andsulfur that dissolved in 0.1N HCl in 20 minutes. Solubility of calciumand sulfur from this product in 0.1 weight percent citric acid was 89%and 94% of the calcium and sulfur that dissolved in 0.1 N HCl in 20minutes. Solubility of calcium and sulfur from this product in 0.2weight percent citric acid was 97% and 100% of the calcium and sulfurthat dissolved in 0.1N HCl in 20 minutes.

Example 24 Polyphosphate Fertilizer with Calcium, Sulfur and ZincEquivalent Ratio Ca:P=0.84:1 and Ca:(P+S)=0.89:1

The fertilizer of this example was produced from phosphoric acid,calcium sulfate (CaSO₄0.5H₂O), zinc oxide and calcium carbonate.Commercial grade phosphoric acid (58.4% P₂0₅), 62.8 grams, was placed ina beaker. Then 30 grams of calcium sulfate and 5 grams of zinc oxidewere mixed with in 60 milliliters of water and the suspension was addedto the phosphoric acid with stirring. The suspension was heated in anoil bath for 20 minutes till the temperature of the liquid reached 110°C. Heating was discontinued and after the suspension cooled to around90° C., it was mixed with a suspension of calcium carbonate in water (57g CaCO₃ in 150 milliliters water). The product was dried in an oven at80° C. and ground in a mortar. It was sieved through a 100 mesh sieve.

On analysis, the product showed 16.1 weight percent phosphorus, 26.2weight percent calcium, 3 weight percent zinc and 5 weight percentsulfur. The ratio of moles of P:Ca was 0.79:1. The pH of a 10%suspension in water was 4.4. Solubility of calcium from this product inwater was 4.4% of the calcium that dissolved in 0.1N HCl in 20 minutes.Solubility of phosphorus from this product in water was 20.4% of thetotal phosphorus. Solubility of calcium and sulfur from this product in0.01 N HCl was 85% and 93% respectively, of the calcium and sulfur thatdissolved in 0.1 N HCl in 20 minutes. Solubility of calcium and sulfurfrom this product in 0.005M EDTA was 95% and 100% of the calcium andsulfur that dissolved in 0.1 N HCl in 20 minutes. Solubility of calciumand sulfur from this product in 0.1 weight percent citric acid was 89%and 94% of the calcium and sulfur that dissolved in 0.1 N HCl in 20minutes.

Example 26 Polyphosphate Fertilizer with Calcium and Zinc EquivalentRatio Ca:P=0.59:1

The fertilizer of this example was produced from phosphoric acid,tricalcium phosphate, zinc oxide and calcium carbonate. Commercial gradephosphoric acid (58.4% P₂0₅), 72.5 grams, was placed in a beaker. Then25 tricalcium phosphate and 5 grams zinc oxide was suspended in 45milliliters of water and the suspension was added to the phosphoric acidwith stirring. It was then heated in an oil bath for 15 minutes till thetemperature of the liquid reached 109° C. The beaker was removed fromthe heating unit and mixed with a suspension of calcium carbonate inwater (50 g CaCO₃ in 100 milliliters water). The product was dried in anoven at 75° C. and ground in a mortar. It was sieved through a 150 meshsieve.

On analysis, the product showed 22 weight percent phosphorus, 25.1weight percent calcium and 3.5 weight percent zinc. The ratio of molesof P:Ca was 1.14:1. The pH of a 10% suspension in water was 4.9.Solubility of calcium and zinc from this product in water was 1.9% and0.3% of the calcium and zinc that dissolved in 0.1N HCl in 20 minutes.Solubility of phosphorus from this product in water was 11.6% of thetotal phosphorus. Solubility of calcium and zinc from this product in0.01 N HCl was 80% and 100% of the calcium and zinc that dissolved in0.1 N HCl in 20 minutes. Solubility of calcium and iron from thisproduct in 0.005M EDTA was 98% and 100% of the calcium and zinc thatdissolved in 0.1N HCl in 20 minutes. Solubility of calcium and zinc thatdissolved from this product in 0.1 weight percent citric acid was 83.5%and 98% of the calcium and zinc that dissolved in 0.1N HCl in 20minutes. The number average chain length of the product excludingorthophosphate was 9.5 and the number average chain length includingortho was 1.47. The orthophosphate content was 36 wt %.

Example 27 Polyphosphate Fertilizer with Calcium (Using TricalciumPhosphate) Equivalent Ratio Ca:P=0.79:1

The fertilizer of this example one was produced from phosphoric acidtricalcium phosphate and calcium carbonate. Commercial grade phosphoricacid (58.4% P₂0₅), 85 grams, was placed in a beaker. In another beaker60 milliliters of water was taken and 25 grams tricalcium phosphate wasadded to it to form a slurry. This slurry was added to the phosphoricacid with stirring. It was then heated in an oil bath for 40 minutestill the temperature of the liquid reached 112° C. Further 10 grams ofphosphoric acid was added and the suspension was heated again to 140° C.

The sample was removed from the oil bath. Then 95 grams of calciumcarbonate was suspended in 150 milliliters of water and added to thereaction mixture with stirring. At this stage a white suspension wasformed and its pH was around 4.5. The product was poured in a dryingdish and dried in an oven at 70° C. After it was dry, the sample wasground and sieved through a 150 mesh sieve.

On analysis, the product showed 22 weight percent phosphorus and 33.7weight percent calcium. The ratio of moles of P:Ca was 0.84:1. The pH ofa 10% suspension in water was 4.5. Solubility of calcium from thisproduct in water was 1.2% of the amount of calcium that dissolves in0.1N HCl in 20 minutes. Solubility of phosphorus from this product inwater was 7.2% of the total phosphorus in it. Solubility of calcium in0.01 N hydrochloric acid and in 0.005M EDTA was 93% and 97%respectively, of the amount of calcium that dissolves in 0.1N HCl in 20minutes. Solubility of calcium in 0.1 wt % citric acid was 86% ofcalcium that dissolved in 20 minutes. The number average chain length ofthe product excluding orthophosphate was 4.2 and the number averagechain length including ortho was 1.92. The orthophosphate content was 32wt %.

Example 28 Polyphosphate Fertilizer with Calcium (Using TricalciumPhosphate) Equivalent Ratio Ca:P=0.76:1

The fertilizer of this example one was produced from phosphoric acidtricalcium phosphate and calcium carbonate. Commercial grade phosphoricacid (58.4% P₂0₅), 95 grams, was placed in a beaker. It was then heatedin an oil bath for 40 minutes till the temperature of the liquid reached175° C. In another beaker 60 milliliters of water was taken and 25 gramstricalcium phosphate was added to it to form a slurry. This slurry wasadded to the phosphoric acid with stirring. It was then heated again to150° C. and then the sample was removed from the oil bath. Then 90 gramsof calcium carbonate was suspended in 150 milliliters of water and addedto the reaction mixture with stirring. At this stage a white suspensionwas formed and its pH was around 4.9. The product was poured in a dryingdish and dried in an oven at 70° C. After it was dry, the sample wasground and sieved through a 150 mesh sieve.

On analysis, the product showed 23 weight percent phosphorus and 30weight percent calcium. The ratio of moles of P:Ca was 0.88:1. The pH ofa 10% suspension in water was 4.9. Solubility of calcium from thisproduct in water was 1% of the amount of calcium that dissolves in 0.1NHCl in 20 minutes. Solubility of phosphorus from this product in waterwas 6.5% of the total phosphorus in it. Solubility of calcium in 0.01 Nhydrochloric acid and in 0.005M EDTA was 90% and 93% respectively, ofthe amount of calcium that dissolves in 0.1N HCl in 20 minutes.Solubility of calcium in 0.1 wt % citric acid was 82% of calcium thatdissolved in 20 minutes. Solubility of calcium in 0.2 wt % citric acidwas 94% of calcium that dissolved in 20 minutes. The number averagechain length of the product excluding orthophosphate was 6.4 and thenumber average chain length including ortho was 2.6. The orthophosphatecontent was 24 wt %.

Prophetic Example Polyphosphate Fertilizer with Calcium and Manganese

The fertilizer of this example would be produced from phosphoric acid,calcium carbonate and manganous oxide. Commercial grade phosphoric acid(58.4% P₂0₅), 71.6 grams, would be placed in a beaker. Then 25.06 gramscalcium carbonate and 1.42 grams manganous oxide suspended in 50milliliters of water would be added to the phosphoric acid withstirring. It would be heated on an oil bath till the liquid becamefairly thick but remained pourable. The liquid temperature at this stagewould be less than 110° C. The liquid would then be neutralized with asuspension of calcium oxide in water with continuous stirring till thepH of the suspension reached 4-5. The product would be dried, ground andsieved.

TABLE 1 Xray Diffraction data Example Example Example Example ExampleExample Example Example Example Example 1 2 3 5 7 9 21 18 17 19 10.15657.6879 15.6121 6.8 18.8003 6.7185 7.5136 7.5612 8.4314 7.5222 9.42896.7243 8.5395 5.96 13.2361 5.0116 6.6765 6.7317 6.7167 4.2153 6.76885.9129 6.7481 5.37 11.6612 4.2598 4.2152 6.2437 4.5098 3.7837 5.96065.3156 6.0223 5.01 8.3331 4.015 3.4706 4.989 4.1387 3.3487 5.3515 5.09185.4567 4.7 6.7121 3.6838 3.3657 4.2278 3.721 3.0345 4.996 4.6937 4.9834.61 5.9122 3.4794 3.3328 3.7872 3.3346 2.9175 4.718 4.59 4.5053 4.55.3858 3.3682 3.1722 3.4728 3.0999 2.8435 4.5016 4.4765 4.4066 4.155.3093 3.118 3.1149 3.3701 2.9447 2.7514 4.4048 4.3732 4.2735 3.7 4.97673.0406 3.0353 3.1197 2.7539 2.7017 4.2803 4.2684 4.1577 3.66 4.88362.9526 2.9477 3.0414 2.7114 2.617 4.1451 4.1346 4.0308 3.58 4.68532.8778 2.9187 2.9543 2.5809 2.5939 4.0367 3.6824 3.7073 3.47 4.58542.7535 2.749 2.8453 2.4886 2.4892 3.7069 3.6448 3.4849 3.39 4.48212.7164 2.7127 2.753 2.2518 2.429 3.4931 3.5687 3.3752 3.35 4.1311 2.57672.6164 2.7177 2.1897 2.252 3.37 3.4564 3.3493 3.19 3.8723 2.493 2.49012.6203 2.1521 2.1657 3.3563 3.367 3.2967 3.13 3.6813 2.346 2.418 2.49022.1109 2.1419 3.1255 3.341 3.1222 3.09 3.5645 2.3001 2.2991 2.4227 2.0912.0801 3.0921 3.3144 2.9567 3.05 3.5318 2.2472 2.2467 2.3026 1.98192.0207 3.0469 3.2842 2.9325 2.96 3.4517 2.1968 2.19 2.2495 1.9079 1.99622.9914 3.1808 2.8805 2.94 3.37 2.1559 2.1515 2.1977 1.8431 1.9706 2.95843.1156 2.7605 2.82 3.3438 2.1336 2.0916 2.1517 1.7185 1.8725 2.93623.0777 2.7221 2.76 3.182 2.1149 2.0269 2.0941 1.6602 1.8536 2.88193.0363 2.6647 2.73 3.1143 2.0682 1.9949 2.0345 1.6052 1.8133 2.75722.9535 2.5841 2.59 3.077 2.0317 1.9102 1.9934 1.7952 2.7279 2.92582.4944 2.53 3.0284 1.9945 1.846 1.9126 1.706 2.5815 2.8104 2.3048 2.52.9449 1.9119 1.8149 1.8465 1.6594 2.5344 2.7821 2.2511 2.43 2.92881.8686 1.7947 1.8146 1.6013 2.4968 2.7538 2.1984 2.41 2.8699 1.84771.7208 1.7949 1.569 2.4081 2.7187 2.1579 2.39 2.8049 1.7969 1.68041.7536 1.5502 2.3522 2.6679 2.1375 2.37 2.7534 1.7526 1.6416 1.72422.3077 2.572 2.1172 2.34 2.7142 1.724 1.6073 1.6883 2.2518 2.5195 2.08642.25 2.6639 1.6929 1.5685 1.607 2.2008 2.4972 2.0326 2.2 2.5764 1.6661.5695 2.1583 2.4283 1.9874 2.18 2.5485 1.6483 2.1418 2.4053 1.9588 2.162.5169 1.6425 2.1192 2.3853 1.9337 2.14 2.4952 1.6075 2.0903 2.36791.9149 2.12 2.387 1.5701 2.0721 2.2964 1.8662 2.09 2.2965 2.0345 2.25011.8507 2.08 2.2466 1.9949 2.197 1.7921 2.03 2.2308 1.9583 2.1714 1.75611.99 2.1947 1.9361 2.1536 1.7257 1.93 2.1552 1.9172 2.1384 1.6919 1.912.1331 1.8869 2.0901 1.6513 1.85 2.1127 1.869 2.0685 1.639 1.8 2.08381.8512 2.0399 1.6093 1.76 2.0277 1.8027 1.9799 1.5713 1.72 1.9923 1.75621.9284 1.68 1.9524 1.7247 1.9112 1.64 1.9116 1.691 1.8853 1.59 1.88241.6796 1.8711 1.847 1.6527 1.8472 1.7924 1.6399 1.7955 1.7545 1.60811.7529 1.7236 1.5702 1.7196 1.6716 1.7027 1.6497 1.6804 1.6371 1.65781.6075 1.637 1.6012 1.5907 1.5617 1.5638

I claim:
 1. A water-insoluble, dilute acid-soluble inorganic polyphosphate composition in solid form, the inorganic polyphosphate composition containing at least 7 wt. % but not more than 35 wt. % calcium, magnesium or a combination thereof and 5 to 70 wt % orthophosphate, the inorganic polyphosphate composition having a number average chain length of greater than 2 but less than 50 repeat units when the orthophosphate content of the inorganic polyphosphate composition is excluded from the average chain length calculation and a number average chain length of at least 1.1 but less than 50 repeat units when the orthophosphate content of the inorganic polyphosphate composition is included in the average chain length calculation, the repeat units comprising phosphate, sulfate, borate, molybdate, or selenate units, or a combination thereof, provided the ratio of phosphate repeat units to the combined total of sulfate, borate, molybdate and selenate repeat units comprised by the inorganic polyphosphate composition is at least 2:1, the water-insoluble, dilute acid-soluble inorganic polyphosphate composition having (i) a solubility in deionized water such that the amount of phosphorus that dissolves from the inorganic polyphosphate composition during a 30 minute period in deionized water at 25° C. is less than 30 wt. % of the amount of phosphorus that dissolves from the inorganic polyphosphate composition during a 30 minute period in 0.1N HCl at 25° C., and (ii) a solubility in dilute citric acid such that the combined amount of calcium and magnesium that dissolves from the inorganic polyphosphate composition during a 20 minute period in 0.2 wt. % citric acid at 25° C. is at least 90 wt. % of the combined amount of calcium and magnesium that dissolves from the inorganic polyphosphate composition during a 20 minute period in 0.1N HCl at 25° C.
 2. The water-insoluble, dilute acid-soluble inorganic polyphosphate composition of claim 1 wherein the inorganic polyphosphate composition contains 7.5 to 50 wt. % orthophosphate.
 3. The water-insoluble, dilute acid-soluble inorganic polyphosphate composition of claim 1 wherein the inorganic polyphosphate composition contains 10 to 30 wt. % orthophosphate.
 4. The water-insoluble, dilute acid-soluble inorganic polyphosphate composition of claim 1 wherein the inorganic polyphosphate composition has a number average chain length of 2.1 to 20 repeat units when the orthophosphate content of the inorganic polyphosphate composition is excluded from the average chain length calculation and a number average chain length of at least 1.2 to 20 repeat units when the orthophosphate content of the inorganic polyphosphate composition is included in the average chain length calculation.
 5. The water-insoluble, dilute acid-soluble inorganic polyphosphate composition of claim 1 wherein the inorganic polyphosphate composition has a number average chain length of 2.5 to 7 repeat units when the orthophosphate content of the inorganic polyphosphate composition is excluded from the average chain length calculation and a number average chain length of at least 1.3 to 4 repeat units when the orthophosphate content of the inorganic polyphosphate composition is included in the average chain length calculation.
 6. The water-insoluble, dilute acid-soluble inorganic polyphosphate composition of claim 1, the inorganic polyphosphate composition containing at least 15 wt. % but not more than 35 wt. % of calcium and magnesium, in combination.
 7. The water-insoluble, dilute acid-soluble inorganic polyphosphate composition of claim 1, the inorganic polyphosphate having a ratio, A:Z, having a value of 0.3:1 to 1.25:1 wherein A is the combined number of equivalents of calcium and magnesium incorporated in the inorganic polyphosphate composition and Z is the combined number of equivalents of phosphorous, boron, molybdenum, and selenium incorporated in the sulfate, borate, molybdate or selenate repeat units.
 8. The water-insoluble, dilute acid-soluble inorganic polyphosphate composition of claim 1, the inorganic polyphosphate composition containing calcium, magnesium, or a combination thereof, and optionally one or more micronutrients selected from boron, chromium, cobalt, copper, iodine, iron, manganese, molybdenum, selenium, and zinc, the inorganic polyphosphate having a ratio, A:P, having a value of 0.3:1 to 1.25:1 wherein A is the combined number of equivalents of calcium and magnesium incorporated in the inorganic polyphosphate composition and P is the number of equivalents of phosphorous, P, incorporated in the inorganic polyphosphate composition.
 9. The water-insoluble, dilute acid-soluble inorganic polyphosphate composition of claim 1, the inorganic polyphosphate composition containing calcium, magnesium, or a combination thereof, and optionally one or more micronutrients selected from boron, chromium, cobalt, copper, iodine, iron, manganese, molybdenum, selenium, and zinc, the inorganic polyphosphate having a ratio, A:P, having a value of 0.3:1 to 1:1 wherein A is the combined number of equivalents of calcium and magnesium incorporated in the inorganic polyphosphate composition and P is the number of equivalents of phosphorous, P, incorporated in the inorganic polyphosphate composition.
 10. The water-insoluble, dilute acid-soluble inorganic polyphosphate composition of claim 1 having a solubility in dilute ethylenediaminetetraacetic acid (EDTA) such that the combined amount of calcium and magnesium that dissolves from the inorganic polyphosphate composition during a 20 minute period in 0.005M EDTA at 25° C. is at least 75% of the combined amount of and magnesium that dissolves from the inorganic polyphosphate composition during a 20 minute period in 0.1N HCl at 25° C.
 11. The water-insoluble, dilute acid-soluble inorganic polyphosphate composition in solid form as further described in claim 1 wherein the atomic ratio of calcium to magnesium is at least 0.2:1 (calcium:magnesium).
 12. The water-insoluble, dilute acid-soluble inorganic polyphosphate composition in solid form as further described in claim 1, the polyphosphate composition containing at least 0.01 wt. % of one or more micronutrients selected from the group consisting of boron, chromium, cobalt, copper, iodine, iron, manganese, molybdenum, selenium and zinc, with the proviso that the inorganic polyphosphate composition contains no more than 3.5 wt. % of such micronutrients, combined, based on the total weight of the polyphosphate.
 13. The water-insoluble, dilute acid-soluble inorganic polyphosphate composition of claim 12 wherein the composition contains no more than 1.5 wt % of the micronutrients, in combination.
 14. The water-insoluble, dilute acid-soluble inorganic polyphosphate composition of claim 12, the inorganic polyphosphate composition containing at least 15 wt. % of calcium.
 15. The water-insoluble, dilute acid-soluble inorganic polyphosphate composition in solid form as further described in claim 1, the polyphosphate composition containing less than 10 wt. % water.
 16. The water-insoluble, dilute acid-soluble inorganic polyphosphate composition in solid form as further described in claim 1, the polyphosphate composition being in the form of free-flowing granules having a particle size that is less than 80 mesh BS.
 17. A fertilizer comprising a water-insoluble, dilute acid-soluble inorganic polyphosphate composition in solid form as further described in claim
 1. 18. The water-insoluble, dilute acid-soluble inorganic polyphosphate composition in solid form as further described in claim 1, wherein the atomic ratio of calcium to magnesium is at 1.25:1 (calcium:magnesium).
 19. The water-insoluble, dilute acid-soluble inorganic polyphosphate composition in solid form as further described in claim 1, the polyphosphate composition containing at least 0.01 wt. % of one or more micronutrients selected from the group consisting of boron, chromium, cobalt, copper, iodine, iron, manganese, molybdenum, selenium and zinc, with the proviso that the inorganic polyphosphate composition contains no more than 15 wt. % of such micronutrients, combined, based on the total weight of the polyphosphate.
 20. The water-insoluble, dilute acid-soluble inorganic polyphosphate composition in solid form as further described in claim 1, the polyphosphate composition containing at least 0.01 wt. % of one or more micronutrients selected from the group consisting of boron, chromium, cobalt, copper, iodine, iron, manganese, molybdenum, selenium and zinc, with the proviso that the inorganic polyphosphate composition contains no more than 10 wt. % of such micronutrients, combined, based on the total weight of the polyphosphate.
 21. The water-insoluble, dilute acid-soluble inorganic polyphosphate composition in solid form as further described in claim 1, the polyphosphate composition containing ammonium.
 22. The water-insoluble, dilute acid-soluble inorganic polyphosphate of claim 21, the polyphosphate composition containing at least 0.01 wt. % of ammonium based on the total weight of the polyphosphate.
 23. The water-insoluble, dilute acid-soluble inorganic polyphosphate of claim 21, the polyphosphate composition containing at least 4 wt. % and no more than 15 wt. % of ammonium based on the total weight of the polyphosphate. 